CN105580192B

CN105580192B - Non-aqueous electrolyte secondary battery

Info

Publication number: CN105580192B
Application number: CN201480053188.4A
Authority: CN
Inventors: 山田淳夫; 山田裕贵; 中垣佳浩; 河合智之; 间濑浩平; 长谷川雄纪; 三好学; 合田信弘; 佐佐木博之; 福本武文
Original assignee: University of Tokyo NUC; Toyoda Automatic Loom Works Ltd
Current assignee: Toyota Industries Corp; University of Tokyo NUC
Priority date: 2013-09-25
Filing date: 2014-09-25
Publication date: 2019-03-12
Anticipated expiration: 2034-09-25
Also published as: KR20160060718A; KR101901676B1; CN105580192A; US20180277852A1; US20160240858A1; DE112014004443T5

Abstract

The purpose of the present invention is to provide the non-aqueous electrolyte secondary batteries that SEI envelope, battery behavior with special construction are excellent.Electrolyte as non-aqueous electrolyte secondary battery, the use of contain with alkali metal, alkaline-earth metal or aluminium is electrolyte cationic and with salt and organic solvent and Is > Io with miscellaneous element that alkali metal, alkaline-earth metal or aluminium are cation, and forms the envelope containing S, O with S=O structure on the surface of anode and/or cathode.In addition, using above-mentioned electrolyte, and use the binder being made of the polymer with hydrophilic radical as cathode binder.

Description

Non-aqueous electrolyte secondary battery

Technical field

The present invention relates to non-aqueous electrolyte secondary batteries.

Background technique

The Surface Creation envelope of the known cathode in non-aqueous electrolyte secondary battery and anode.The envelope is also referred to as SEI (Solid Electrolyte Interphase: solid electrolyte interface film) constitutes (example by reduction decomposition object of electrolyte etc. Such as, referring to patent document 1).Hereinafter, according to circumstances, which is referred to as SEI envelope.

The SEI envelope of negative terminal surface and positive electrode surface allows passing through for lithium ion electrical charge carrier.Additionally, it is believed that for example negative The SEI envelope of pole surface is present between negative terminal surface and electrolyte, facilitates the further reduction decomposition for inhibiting electrolyte.It is special It is not for the low potential cathode for having used the negative electrode active material of graphite, Si system, SEI envelope is necessary.

Think to can be improved after circulation if inhibiting electrolyte to continue to decompose since SEI envelope exists The flash-over characteristic (hereinafter referred to as cycle characteristics) of battery.However its another aspect, for existing non-aqueous electrolyte secondary battery For, it can not say that the SEI envelope of negative terminal surface and positive electrode surface centainly facilitates the raising of battery behavior.Therefore, it is intended that opening Issue a kind of non-aqueous electrolyte secondary battery with the SEI envelope that battery behavior can be made to further increase.

On the other hand, such as lithium ion secondary battery is charge/discharge capacity height, the secondary cell for capableing of high-output power. Lithium ion secondary battery is primarily now used as portable electronic device, laptop, power supply for electric vehicle, needs smaller The light-duty secondary cell of type.Especially in mobile applications, due to needing to carry out the charge and discharge of lithium ion secondary battery with high current Electricity it requires and develop a kind of lithium ion secondary battery with high input-output characteristic.

The anode and cathode of lithium ion secondary battery are respectively provided with the active material that can occlude and release lithium (Li).And It and is to move to work in the electrolyte for being sealed in two interpolars by lithium ion.In order to improve the lithiums such as input-output characteristic The battery behavior of ion secondary battery needs to improve active material used in anode and/or cathode, binder and improves electricity Solve liquid etc..

Make extensively the problem of precipitation in order to avoid skeleton as the negative electrode active material of lithium ion secondary battery With carbon materials such as graphite.In order to make lithium ion reversibly be inserted into and be detached from, general electrolyte to such negative electrode active material The middle carbonate-based solvent using non-water systems such as cyclic ester, chain esters.However for using the existing electricity of carbonate-based solvent For solution liquid, it is difficult to greatly improve a kind of multiplying power property of the input-output characteristic as lithium ion secondary battery.That is, as follows Described in the non-patent literature 1~3 stated, the lithium ion secondary of the carbonate-based solvents such as ethylene carbonate, propylene carbonate has been used Reaction resistance is big in battery.Therefore, in order to improve rate capability characteristic, need fundamentally to rethink the solvent group of electrolyte At.

Existing technical literature

Patent document

Patent document 1: Japanese Unexamined Patent Publication 2007-19027 bulletin

Patent document 2: Japanese Unexamined Patent Publication 2007-115671 bulletin

Patent document 3: Japanese Unexamined Patent Publication 2003-268053 bulletin

Patent document 4: Japanese Unexamined Patent Publication 2006-513554 bulletin

Non-patent literature

Non-patent literature 1:T.Abe et al., J.Electrochem.Soc., 151, A1120-A1123 (2004)

Non-patent literature 2:T.Abe et al., J.Electrochem.Soc., 152, A2151-A2154 (2005)

Non-patent literature 3:Y.Yamada et al., Langmuir, 25,12766-12770 (2009)

Summary of the invention

The present invention considers above situation and carries out, and the project to be solved is to obtain the excellent non-water power of battery behavior Solve electrolitc secondary cell.

The Surface Creation envelope of the known cathode in non-aqueous electrolyte secondary battery and anode.The envelope is also referred to as SEI (Solid Electrolyte Interphase), is made of reduction decomposition object of electrolyte etc..For example, Japanese Unexamined Patent Publication 2007- The envelope is also described in No. 19027 bulletins.Hereinafter, according to circumstances, which is referred to as SEI envelope.

The present inventor etc. passes through further investigation, as a result, it has been found that in existing non-aqueous electrolyte secondary battery, root Passability according to the composition of SEI envelope, structure, thickness lithium ion electrical charge carrier sometimes is insufficient, and SEI envelope can become non-aqueous The reaction resistance of electrolyte secondary battery increases the reason of (such as reduction of input-output characteristic).In this way, having to develop Be able to suppress electrolyte continue to decompose and the non-aqueous electrolyte secondary battery of the permeability of charge carrier also excellent SEI envelope For target, further research is made.Finally, it is found that in the non-aqueous electrolyte secondary battery using special electrolyte, The SEI envelope of the special construction from the electrolyte is generated in negative terminal surface.In addition, it has further been found that also generated in positive electrode surface The SEI envelope of special construction from the electrolyte.And it is found to have the electrolyte and the special construction from the electrolyte The battery behaviors such as service life, the input-output characteristic of non-aqueous electrolyte secondary battery of SEI envelope it is excellent.

That is, the non-aqueous electrolyte secondary battery (1) of the invention for solving the above subject includes anode, electrolyte and cathode,

Above-mentioned electrolyte contains salt and the organic solvent with miscellaneous element, which is sun with alkali metal, alkaline-earth metal or aluminium Ion and in the chemical structure of anion contain element sulphur and oxygen element,

For the peak intensity from above-mentioned organic solvent in the vibrational spectrum of above-mentioned electrolyte, by above-mentioned organic solvent sheet When the intensity at the peak come is set as Io, the intensity at the peak after above-mentioned peak shift is set as Is, meet Is > Io,

The envelope containing S, O with S=O structure is formd on the surface of above-mentioned cathode.

In addition, the non-aqueous electrolyte secondary battery (1) of the invention for solving the above subject includes anode, electrolyte and bears Pole,

For the peak intensity from above-mentioned organic solvent in the vibrational spectrum of above-mentioned electrolyte, by above-mentioned organic solvent sheet When the intensity at the peak come is set as Io, the intensity that above-mentioned peak generates the peak after displacement is set as Is, meet Is > Io,

The surface of at least the above anode in the surface of above-mentioned cathode and the surface of above-mentioned anode is formd with S=O The envelope containing S, O of structure.

Such non-aqueous electrolyte secondary battery (1) has the SEI quilt of special construction in negative terminal surface and/or positive electrode surface Film, the i.e. envelope containing S, O, battery behavior are excellent.

On the other hand, general cathode is by being coated with the slurry containing negative electrode active material and binder simultaneously in collector It is dry and production.Binder has the work for making to bond between negative electrode active material and make to bond between active material and collector With the effect of, covering protection negative electrode active material.

As the cathode binder used in the past, there is Kynoar (PVdF) etc. fine containing fluorine system polymer, carboxymethyl Tie up water-soluble cellulose derivatives, polyacrylic acid such as plain (CMC) etc..Such as in above-mentioned patent document 2, describe containing choosing From the polymer in polyacrylic acid and polymethylacrylic acid and the polymer contains the lithium ion secondary battery cathode of anhydride group. In addition, describing in above-mentioned patent document 3 and using polymer obtained by acrylic acid and methacrylic acid copolymer as cathode Binder or anode binder.In addition, describing in above-mentioned patent document 4 by acrylamide and acrylic acid and clothing health Polymer obtained by acid copolymerization is used as cathode binder or anode binder.

The feature for solving the non-aqueous electrolyte secondary battery (2) of the invention of the above subject has electrolyte and cathode,

Above-mentioned electrolyte contains with alkali metal, alkaline-earth metal or aluminium for the salt of cation and with the organic molten of miscellaneous element The intensity at the original peak of above-mentioned organic solvent is set as the peak intensity from above-mentioned organic solvent in vibrational spectrum by agent Io, when the intensity at the peak after above-mentioned peak shift is set as Is, meet Is > Io,

Above-mentioned cathode has the negative electrode active material layer containing binder, and the binder is by the polymer with hydrophilic radical It constitutes.

Non-aqueous electrolyte secondary battery (2) of the invention uses bonding of the polymer with hydrophilic radical as cathode Agent, and use electrolyte of the invention as electrolyte.Use the polymer such as Kynoar as the binder of cathode When, even with identical electrolyte of the invention, it is also difficult to have both the raising of multiplying power property and the raising of cycle characteristics.But It is that, by using the binder being made of the polymer with hydrophilic radical as cathode binder, multiplying power spy can be had both The raising of property and the raising of cycle characteristics.It is following to consider as its reason: for example, if non-aqueous electrolyte secondary battery be lithium from Sub- secondary cell, then the carboxyl isopolarity group as contained by binder attracts lithium ion, so dominated in concentration overvoltage High magnification side part throttle characteristics improves.It is additionally contemplated that the active material protective effect that binder generates improves cycle characteristics.

That is, if utilizing electrolyte and binder most using such non-aqueous electrolyte secondary battery (2) It is good to combine the raising that can be realized rate capability characteristic, and cycle characteristics can also be improved.

Hereinafter, as needed, sometimes will " containing with alkali metal, alkaline-earth metal or aluminium be cation salt and have miscellaneous member The organic solvent of element, and for the peak intensity from above-mentioned organic solvent in vibrational spectrum, originally by above-mentioned organic solvent When the intensity at peak is set as Io, the intensity at the peak after above-mentioned peak shift is set as Is, meet the electrolyte of Is > Io " it is known as " this hair Bright electrolyte ".

In addition, sometimes will in above-mentioned electrolyte of the invention in the chemical structure of the anion of salt containing element sulphur and The electrolyte of oxygen element is especially referred to as " electrolyte (1) " or " electrolyte (1) of the invention ".Electrolyte (1) of the invention is this One kind of the electrolyte of invention contains in above-mentioned non-aqueous electrolyte secondary battery (1).Certainly, non-aqueous electrolyte secondary battery (2) electrolyte (1) of the invention can also be contained.

In addition, as needed, non-aqueous electrolyte secondary battery (1) and non-aqueous electrolyte secondary battery (2) are referred to as this The non-aqueous electrolyte secondary battery of invention.

The battery behavior of non-aqueous electrolyte secondary battery of the invention is excellent.

Detailed description of the invention

Fig. 1 is the IR spectrum of electrolyte E3.

Fig. 2 is the IR spectrum of electrolyte E4.

Fig. 3 is the IR spectrum of electrolyte E7.

Fig. 4 is the IR spectrum of electrolyte E8.

Fig. 5 is the IR spectrum of electrolyte E10.

Fig. 6 is the IR spectrum of electrolyte C2.

Fig. 7 is the IR spectrum of electrolyte C4.

Fig. 8 is the IR spectrum of acetonitrile.

Fig. 9 is (CF₃SO₂)₂The IR spectrum of NLi.

Figure 10 is (FSO₂)₂The IR spectrum of NLi.

Figure 11 is the IR spectrum of electrolyte E11.

Figure 12 is the IR spectrum of electrolyte E12.

Figure 13 is the IR spectrum of electrolyte E13.

Figure 14 is the IR spectrum of electrolyte E14.

Figure 15 is the IR spectrum of electrolyte E15.

Figure 16 is the IR spectrum of electrolyte C6.

Figure 17 is the IR spectrum of dimethyl carbonate.

Figure 18 is the IR spectrum of electrolyte E16.

Figure 19 is the IR spectrum of electrolyte E17.

Figure 20 is the IR spectrum of electrolyte E18.

Figure 21 is the IR spectrum of electrolyte C7.

Figure 22 is the IR spectrum of methyl ethyl carbonate.

Figure 23 is the IR spectrum of electrolyte E19.

Figure 24 is the IR spectrum of electrolyte E20.

Figure 25 is the IR spectrum of electrolyte E21.

Figure 26 is the IR spectrum of electrolyte C8.

Figure 27 is the IR spectrum of diethyl carbonate.

Figure 28 is (FSO₂)₂IR spectrum (1900~1600cm of NLi^-1)。

Figure 29 is the Raman spectrum of electrolyte E8.

Figure 30 is the Raman spectrum of electrolyte E9.

Figure 31 is the Raman spectrum of electrolyte C4.

Figure 32 is the Raman spectrum of electrolyte E11.

Figure 33 is the Raman spectrum of electrolyte E13.

Figure 34 is the Raman spectrum of electrolyte E15.

Figure 35 is the Raman spectrum of electrolyte C6.

Figure 36 is the result for evaluating the responsiveness to fast charging and discharging repeatedly of example 8.

Figure 37 be evaluate example 12 in the cathode for embodiment 1-1, embodiment 1-2 and comparative example 1-1 containing S, O envelope The XPS analysis result of carbon.

Figure 38 be evaluate example 12 in the cathode for embodiment 1-1, embodiment 1-2 and comparative example 1-1 containing S, O envelope The XPS analysis result of fluorine element.

Figure 39 be evaluate example 12 in the cathode for embodiment 1-1, embodiment 1-2 and comparative example 1-1 containing S, O envelope The XPS analysis result of nitrogen.

Figure 40 be evaluate example 12 in the cathode for embodiment 1-1, embodiment 1-2 and comparative example 1-1 containing S, O envelope The XPS analysis result of oxygen element.

Figure 41 be evaluate example 12 in the cathode for embodiment 1-1, embodiment 1-2 and comparative example 1-1 containing S, O envelope The XPS analysis result of element sulphur.

Figure 42 is XPS analysis result of the cathode containing S, O envelope for evaluating the embodiment 1-1 in example 12.

Figure 43 is XPS analysis result of the cathode containing S, O envelope for evaluating the embodiment 1-2 in example 12.

Figure 44 is BF-STEM image of the cathode containing S, O envelope for evaluating the embodiment 1-1 in example 12.

Figure 45 is STEM analysis result of the cathode for embodiment 1-1 containing the C of S, O envelope evaluated in example 12.

Figure 46 is STEM analysis result of the cathode for embodiment 1-1 containing the O of S, O envelope evaluated in example 12.

Figure 47 is STEM analysis result of the cathode for embodiment 1-1 containing the S of S, O envelope evaluated in example 12.

Figure 48 is the XPS analysis result for evaluating O of the anode containing S, O envelope for embodiment 1-1 in example 12.

Figure 49 is the XPS analysis result for evaluating S of the anode containing S, O envelope for embodiment 1-1 in example 12.

Figure 50 is the XPS analysis result for evaluating S of the anode containing S, O envelope for embodiment 1-4 in example 12.

Figure 51 is the XPS analysis result for evaluating O of the anode containing S, O envelope for embodiment 1-4 in example 12.

Figure 52 is to evaluate the anode for embodiment 1-4, embodiment 1-5 and comparative example 1-2 in example 12 containing S, O envelope The XPS analysis result of S.

Figure 53 is to evaluate the anode for embodiment 1-6, embodiment 1-7 and comparative example 1-3 in example 12 containing S, O envelope The XPS analysis result of S.

Figure 54 is to evaluate the anode for embodiment 1-4, embodiment 1-5 and comparative example 1-2 in example 12 containing S, O envelope The XPS analysis result of O.

Figure 55 is to evaluate the anode for embodiment 1-6, embodiment 1-7 and comparative example 1-3 in example 12 containing S, O envelope The analysis result of O.

Figure 56 be evaluate example 12 in the cathode for embodiment 1-4, embodiment 1-5 and comparative example 1-2 containing S, O envelope The analysis result of S.

Figure 57 be evaluate example 12 in the cathode for embodiment 1-6, embodiment 1-7 and comparative example 1-3 containing S, O envelope The analysis result of S.

Figure 58 be evaluate example 12 in the cathode for embodiment 1-4, embodiment 1-5 and comparative example 1-2 containing S, O envelope The analysis result of O.

Figure 59 be evaluate example 12 in the cathode for embodiment 1-6, embodiment 1-7 and comparative example 1-3 containing S, O envelope The analysis result of O.

Figure 60 is the complex impedance plane curve for evaluating the battery in example 13.

Figure 61 is the DSC chart for evaluating the non-aqueous electrolyte secondary battery of the embodiment 1-1 in example 20.

Figure 62 is the DSC chart for evaluating the non-aqueous electrolyte secondary battery of the comparative example 1-1 in example 20.

Figure 63 is the figure for indicating the relationship of electric current and electrode potential of the EB4 in evaluation example 21.

Figure 64 is the figure for indicating the relationship of the current potential (3.1~4.6V) and response current for EB4 in evaluation example 22.

Figure 65 is the figure for indicating the relationship of the current potential (3.1~5.1V) and response current for EB4 in evaluation example 22.

Figure 66 is the figure for indicating the relationship of the current potential (3.1~4.6V) and response current for EB5 in evaluation example 22.

Figure 67 is the figure for indicating the relationship of the current potential (3.1~5.1V) and response current for EB5 in evaluation example 22.

Figure 68 is the figure for indicating the relationship of the current potential (3.1~4.6V) and response current for EB6 in evaluation example 22.

Figure 69 is the figure for indicating the relationship of the current potential (3.1~5.1V) and response current for EB6 in evaluation example 22.

Figure 70 is the figure for indicating the relationship of the current potential (3.1~4.6V) and response current for EB7 in evaluation example 22.

Figure 71 is the figure for indicating the relationship of the current potential (3.1~5.1V) and response current for EB7 in evaluation example 22.

Figure 72 is the figure for indicating the relationship of the current potential (3.1~4.6V) and response current for CB4 in evaluation example 22.

Figure 73 is the figure for indicating the relationship of the current potential (3.0~4.5V) and response current for EB5 in evaluation example 22.It answers Explanation is given, Figure 73 is the figure for changing the scale bar of the longitudinal axis of Figure 66 and obtaining.

Figure 74 is the figure for indicating the relationship of the current potential (3.0~5.0V) and response current for EB5 in evaluation example 22.It answers Explanation is given, Figure 74 is the figure for changing the scale bar of the longitudinal axis of Figure 67 and obtaining.

Figure 75 is the figure for indicating the relationship of the current potential (3.0~4.5V) and response current for EB8 in evaluation example 22.

Figure 76 is the figure for indicating the relationship of the current potential (3.0~5.0V) and response current for EB8 in evaluation example 22.

Figure 77 is the figure for indicating the relationship of the current potential (3.0~4.5V) and response current for CB5 in evaluation example 22.

Figure 78 is the figure for indicating the relationship of the current potential (3.0~5.0V) and response current for CB5 in evaluation example 22.

Figure 79 is the surface of the aluminium foil after the charge and discharge of the non-aqueous electrolyte secondary battery of the embodiment 1-1 in evaluation example 24 Analyze result.

Figure 80 is the surface of the aluminium foil after the charge and discharge of the non-aqueous electrolyte secondary battery of the embodiment 1-2 in evaluation example 24 Analyze result.

Figure 81 is the charging and discharging curve of EB9.

Figure 82 is the charging and discharging curve of EB10.

Figure 83 is the charging and discharging curve of EB11.

Figure 84 is the charging and discharging curve of EB12.

Figure 85 is the charging and discharging curve of CB6.

Figure 86 is the result for evaluating the low temperature multiplying power property of example 29.

Figure 87 is the result for evaluating the low temperature multiplying power property of example 29.

Figure 88 is the charge-discharge characteristic for indicating the non-aqueous electrolyte secondary battery of embodiment 2-1,2-2 and comparative example 2-1 Figure.

Specific embodiment

Hereinafter, being illustrated to mode for carrying out the present invention.It should be noted that unless otherwise specified, then this theory The numberical range " a~b " recorded in bright book refers within its scope comprising lower limit a and upper limit b.Moreover, further including these upper limits The numerical value enumerated in value and lower limit value and embodiment, by the way that these numerical value any combination may make up numberical range.And then from Optional numerical value can be the upper limit, the numerical value of lower limit in numberical range.

Non-aqueous electrolyte secondary battery (1) of the invention includes cathode, anode and electrolyte of the invention (1), in anode And/or the surface of cathode is formd containing S, O envelope.In addition, non-aqueous electrolyte secondary battery (2) of the invention includes of the invention Electrolyte and the cathode for having negative electrode active material layer, the negative electrode active material layer contain by the polymer structure with hydrophilic radical At binder.

As described above, being formd in non-aqueous electrolyte secondary battery (1) of the invention on the surface of anode and/or cathode Containing S, O envelope, the raising of battery behavior is realized.Therefore, the battery structure in non-aqueous electrolyte secondary battery (1) in addition to electrolyte At element, such as negative electrode active material, positive active material, conductive auxiliary agent, binder, collector and separator etc. without special It limits.In addition, as described above, in non-aqueous electrolyte secondary battery (2) of the invention, cathode binder and electrolyte are utilized The raising of optimal combination realization battery behavior.Therefore, cathode binder and electrolyte are removed in non-aqueous electrolyte secondary battery (2) Battery constituent element in addition is not particularly limited.It is negative in non-aqueous electrolyte secondary battery of the invention under either case Pole surface and/or positive electrode surface are respectively formed the SEI envelope of special construction, the i.e. envelope containing S, O.

In addition, the charge carrier in non-aqueous electrolyte secondary battery of the invention is also not particularly limited.For example, of the invention Non-aqueous electrolyte secondary battery can be using lithium as charge carrier non-aqueous electrolyte secondary battery (for example, lithium secondary battery, Lithium ion secondary battery), can be using sodium as charge carrier non-aqueous electrolyte secondary battery (for example, sodium rechargeable battery, sodium from Sub- secondary cell).

As described above, electrolyte of the invention contains with alkali metal, alkaline-earth metal or aluminium for the salt of cation and with miscellaneous The organic solvent of atom, for the peak intensity from organic solvent in vibrational spectrum, by the intensity at the original peak of organic solvent When being set as Io, the intensity that the original peak of organic solvent generates the peak after wave number displacement being set as Is, meet Is > Io.In addition, its In, electrolyte (1) use used in non-aqueous electrolyte secondary battery (1) with alkali metal, alkaline-earth metal or aluminium be cation and Contain the salt of element sulphur and oxygen element in the chemical structure of anion as salt.That is, electrolyte (1) is electricity of the invention Solve a mode of liquid.As long as being therefore electrolyte of the invention, the relationship of Io and Is are usually Is > Io.In contrast, The relationship of existing electrolyte, Is and Io are Is < Io.Electrolyte of the invention and existing electrolyte have very big in this regard It is different.Hereinafter, as needed, by salt contained by electrolyte and/or electrolyte (1) of the invention, that is, " with alkali metal, alkaline earth gold Belong to or aluminium be the salt of cation " and/or " with alkali metal, alkaline-earth metal or aluminium be cationic and in the chemical structure of anion Salt containing element sulphur and oxygen element " is sometimes referred to as " metal salt ", supports salt, supporting electrolyte or be referred to as " salt ".It should say It is bright, since electrolyte (1) is a mode of electrolyte of the invention, so right in the case where being not particularly illustrated, explaining The position that " electrolyte of the invention " is illustrated is exactly to carry out to comprising the electrolyte whole of the invention including electrolyte (1) Explanation.

(metal salt)

As long as LiClO contained by electrolyte of the metal salt in electrolyte of the invention usually as battery₄、LiAsF₆、 LiPF₆、LiBF₄、LiAlCl₄The compound that equal electrolyte use.As the cation of metal salt, lithium, sodium, potassium can be enumerated Equal alkali metal, the alkaline-earth metal such as beryllium, magnesium, calcium, strontium, barium and aluminium.The cation of metal salt is preferably and the battery that uses electrolyte The identical metal ion of charge carrier.For example, if using electrolyte of the invention as the electricity of lithium ion secondary battery Liquid is solved, then the cation of metal salt is preferably lithium.

At this point, it is preferred that the chemical structure of the anion of salt contains selected from least one of halogen, boron, nitrogen, oxygen, sulphur or carbon Element.Particular instantiation contains the chemical structure of the anion of halogen or boron, can enumerate ClO₄、PF₆、AsF₆、SbF₆、TaF₆、BF₄、 SiF₆、B(C₆H₅)₄、B(oxalate)₂、Cl、Br、I。

For the chemical structure of the anion containing nitrogen, oxygen, sulphur or carbon, it is specifically described below.

The chemical structure of the anion of salt is preferably the chemical structure that the following general formula (1), general formula (2) or general formula (3) indicate.

(R¹X¹)(R²X²) N general formula (1)

(R¹Selected from hydrogen, halogen, the alkyl that can be substituted with a substituent, the naphthenic base that can be substituted with a substituent, can be by The unsaturated alkyl of substituent group substitution, the unsaturated ring alkyl that can be substituted with a substituent, the fragrance that can be substituted with a substituent Race's group, the alkoxy that can be substituted with a substituent, can be substituted with a substituent not the heterocycle that can be substituted with a substituent Saturation alkoxy, can be substituted with a substituent thio alkoxy, can be substituted with a substituent unsaturated thio alkoxy, CN、SCN、OCN。

R²Selected from hydrogen, halogen, the alkyl that can be substituted with a substituent, the naphthenic base that can be substituted with a substituent, can be by The unsaturated alkyl of substituent group substitution, the unsaturated ring alkyl that can be substituted with a substituent, the fragrance that can be substituted with a substituent Race's group, the alkoxy that can be substituted with a substituent, can be substituted with a substituent not the heterocycle that can be substituted with a substituent Saturation alkoxy, can be substituted with a substituent thio alkoxy, can be substituted with a substituent unsaturated thio alkoxy, CN、SCN、OCN。

In addition, R¹And R²It can be mutually bonded and form ring.

X¹Selected from SO₂, C=O, C=S, R^aP=O, R^bP=S, S=O, Si=O.

X²Selected from SO₂, C=O, C=S, R^cP=O, R^dP=S, S=O, Si=O.

R^a、R^b、R^c、R^dIt is each independently selected from hydrogen, halogen, the alkyl that can be substituted with a substituent, base can be substituted takes The naphthenic base in generation, the unsaturated alkyl that can be substituted with a substituent, the unsaturated ring alkyl that can be substituted with a substituent, can be by Aromatic group that substituent group replaces, the heterocycle that can be substituted with a substituent, the alkoxy that can be substituted with a substituent, can be with The unsaturated alkoxy that is substituted with a substituent, can be substituted with a substituent not the thio alkoxy that can be substituted with a substituent It is saturated thio alkoxy, OH, SH, CN, SCN, OCN.

In addition, R^a、R^b、R^c、R^dIt can be with R¹Or R²It is bonded and forms ring.)

R³X³Y general formula (2)

(R³Selected from hydrogen, halogen, the alkyl that can be substituted with a substituent, the naphthenic base that can be substituted with a substituent, can be by The unsaturated alkyl of substituent group substitution, the unsaturated ring alkyl that can be substituted with a substituent, the fragrance that can be substituted with a substituent Race's group, the alkoxy that can be substituted with a substituent, can be substituted with a substituent not the heterocycle that can be substituted with a substituent Saturation alkoxy, can be substituted with a substituent thio alkoxy, can be substituted with a substituent unsaturated thio alkoxy, CN、SCN、OCN。

X³Selected from SO₂, C=O, C=S, R^eP=O, R^fP=S, S=O, Si=O.

R^e、R^fIt is each independently selected from hydrogen, halogen, the alkyl that can be substituted with a substituent, the ring that can be substituted with a substituent Alkyl, the unsaturated ring alkyl that can be substituted with a substituent, can be substituted base at the unsaturated alkyl that can be substituted with a substituent Substituted aromatic group, the alkoxy that can be substituted with a substituent, can be substituted the heterocycle that can be substituted with a substituent The unsaturated alkoxy of base substitution, the thio alkoxy that can be substituted with a substituent, the unsaturated sulphur that can be substituted with a substituent For alkoxy, OH, SH, CN, SCN, OCN.

In addition, R^e、R^fIt can be with R³It is bonded and forms ring.

Y is selected from O, S.)

(R⁴X⁴)(R⁵X⁵)(R⁶X⁶) C general formula (3)

(R⁴Selected from hydrogen, halogen, the alkyl that can be substituted with a substituent, the naphthenic base that can be substituted with a substituent, can be by The unsaturated alkyl of substituent group substitution, the unsaturated ring alkyl that can be substituted with a substituent, the fragrance that can be substituted with a substituent Race's group, the alkoxy that can be substituted with a substituent, can be substituted with a substituent not the heterocycle that can be substituted with a substituent Saturation alkoxy, can be substituted with a substituent thio alkoxy, can be substituted with a substituent unsaturated thio alkoxy, CN、SCN、OCN。

R⁵Selected from hydrogen, halogen, the alkyl that can be substituted with a substituent, the naphthenic base that can be substituted with a substituent, can be by The unsaturated alkyl of substituent group substitution, the unsaturated ring alkyl that can be substituted with a substituent, the fragrance that can be substituted with a substituent Race's group, the alkoxy that can be substituted with a substituent, can be substituted with a substituent not the heterocycle that can be substituted with a substituent Saturation alkoxy, can be substituted with a substituent thio alkoxy, can be substituted with a substituent unsaturated thio alkoxy, CN、SCN、OCN。

R⁶Selected from hydrogen, halogen, the alkyl that can be substituted with a substituent, the naphthenic base that can be substituted with a substituent, can be by The unsaturated alkyl of substituent group substitution, the unsaturated ring alkyl that can be substituted with a substituent, the fragrance that can be substituted with a substituent Race's group, the alkoxy that can be substituted with a substituent, can be substituted with a substituent not the heterocycle that can be substituted with a substituent Saturation alkoxy, can be substituted with a substituent thio alkoxy, can be substituted with a substituent unsaturated thio alkoxy, CN、SCN、OCN。

In addition, R⁴、R⁵、R⁶In wantonly two or three can be bonded and form ring.

X⁴Selected from SO₂, C=O, C=S, R^gP=O, R^hP=S, S=O, Si=O.

X⁵Selected from SO₂, C=O, C=S, RⁱP=O, R^jP=S, S=O, Si=O.

X⁶Selected from SO₂, C=O, C=S, R^kP=O, R^lP=S, S=O, Si=O.

R^g、R^h、Rⁱ、R^j、R^k、R^lIt is each independently selected from hydrogen, halogen, the alkyl that can be substituted with a substituent, can be taken For base replace naphthenic base, can be substituted with a substituent unsaturated alkyl, can be substituted with a substituent unsaturated ring alkyl, The aromatic group that can be substituted with a substituent, the heterocycle that can be substituted with a substituent, the alcoxyl that can be substituted with a substituent Base, the thio alkoxy that can be substituted with a substituent, can be substituted base and take the unsaturated alkoxy that can be substituted with a substituent Unsaturated thio alkoxy, OH, SH, CN, SCN, the OCN in generation.

In addition, R^g、R^h、Rⁱ、R^j、R^k、R^lIt can be with R⁴、R⁵Or R⁶It is bonded and forms ring.)

" can be substituted with a substituent " the words in chemical structure indicated above-mentioned general formula (1)~(3) is said It is bright.For example, if being " alkyl that can be substituted with a substituent ", then refer to what one or more hydrogen of alkyl were substituted with a substituent Alkyl or alkyl without special substituent group.

As the substituent group in " can be substituted with a substituent " the words, can enumerate alkyl, alkenyl, alkynyl, naphthenic base, Unsaturated ring alkyl, aromatic group, heterocycle, halogen, OH, SH, CN, SCN, OCN, nitro, alkoxy, unsaturated alcoxyl Base, amino, alkyl amino, dialkyl amido, aryloxy group, acyl group, alkoxy carbonyl, acyloxy, aryloxycarbonyl, acyloxy, Acyl amino, alkoxycarbonyl amino, aryloxycarbonylamino, sulfuryl amino, sulfamoyl, carbamoyl, alkyl sulfide Base, artyl sulfo, sulfonyl, sulfinyl, urea groups, phosphoamide base, sulfo group, carboxyl, hydroxamic acid base, sulfino, diazanyl, Imino group, silicyl etc..These substituent groups can be further substituted.In addition when substituent group is 2 or more, substituent group can be with It is identical to can also be different.

The chemical structure that more preferable the following general formula of the chemical structure of the anion of salt (4), general formula (5) or general formula (6) indicate.

(R⁷X⁷)(R⁸X⁸) N general formula (4)

(R⁷、R⁸It is each independently C_nH_aF_bCl_cBr_dI_e(CN)_f(SCN)_g(OCN)h。

N, a, b, c, d, e, f, g, h are each independently 0 or more integer, meet 2n+1=a+b+c+d+e+f+g+h.

In addition, R⁷And R⁸It can be mutually bonded and form ring, at this point, meeting 2n=a+b+c+d+e+f+g+h.

X⁷Selected from SO₂, C=O, C=S, R^mP=O, RⁿP=S, S=O, Si=O.

X⁸Selected from SO₂, C=O, C=S, R^oP=O, R^pP=S, S=O, Si=O.

R^m、Rⁿ、R^o、R^pIt is each independently selected from hydrogen, halogen, the alkyl that can be substituted with a substituent, base can be substituted takes The naphthenic base in generation, the unsaturated alkyl that can be substituted with a substituent, the unsaturated ring alkyl that can be substituted with a substituent, can be by Aromatic group that substituent group replaces, the heterocycle that can be substituted with a substituent, the alkoxy that can be substituted with a substituent, can be with The unsaturated alkoxy that is substituted with a substituent, can be substituted with a substituent not the thio alkoxy that can be substituted with a substituent It is saturated thio alkoxy, OH, SH, CN, SCN, OCN.

In addition, R^m、Rⁿ、R^o、R^pIt can be with R⁷Or R⁸It is bonded and forms ring.)

R⁹X⁹Y general formula (5)

(R⁹For C_nH_aF_bCl_cBr_dI_e(CN)_f(SCN)_g(OCN)_h。

X⁹Selected from SO₂, C=O, C=S, R^qP=O, R^rP=S, S=O, Si=O.

R^q、R^rIt is each independently selected from hydrogen, halogen, the alkyl that can be substituted with a substituent, the ring that can be substituted with a substituent Alkyl, the unsaturated ring alkyl that can be substituted with a substituent, can be substituted base at the unsaturated alkyl that can be substituted with a substituent Substituted aromatic group, the alkoxy that can be substituted with a substituent, can be substituted the heterocycle that can be substituted with a substituent The unsaturated alkoxy of base substitution, the thio alkoxy that can be substituted with a substituent, the unsaturated sulphur that can be substituted with a substituent For alkoxy, OH, SH, CN, SCN, OCN.

In addition, R^q、R^rIt can be with R⁹It is bonded and forms ring.

Y is selected from O, S.)

(R¹⁰X¹⁰)(R¹¹X¹¹)(R¹²X¹²) C general formula (6)

(R¹⁰、R¹¹、R¹²It is each independently C_nH_aF_bCl_cBr_dI_e(CN)_f(SCN)_g(OCN)_h。

R¹⁰、R¹¹、R¹²In wantonly two can be bonded and form ring, at this point, formed ring group meet 2n=a+b+c+d+e+ f+g+h.In addition, R¹⁰、R¹¹、R¹²Three can be bonded and form ring, at this point, two groups meet 2n=a+b+c+d+e in three + f+g+h, a group meet 2n-1=a+b+c+d+e+f+g+h.

X¹⁰Selected from SO₂, C=O, C=S, R^sP=O, R^tP=S, S=O, Si=O.

X¹¹Selected from SO₂, C=O, C=S, R^uP=O, R^vP=S, S=O, Si=O.

X¹²Selected from SO₂, C=O, C=S, R^wP=O, R^xP=S, S=O, Si=O.

R^s、R^t、R^u、R^v、R^w、R^xIt is each independently selected from hydrogen, halogen, the alkyl that can be substituted with a substituent, can be taken For base replace naphthenic base, can be substituted with a substituent unsaturated alkyl, can be substituted with a substituent unsaturated ring alkyl, The aromatic group that can be substituted with a substituent, the heterocycle that can be substituted with a substituent, the alcoxyl that can be substituted with a substituent Base, the thio alkoxy that can be substituted with a substituent, can be substituted base and take the unsaturated alkoxy that can be substituted with a substituent Unsaturated thio alkoxy, OH, SH, CN, SCN, the OCN in generation.

In addition, R^s、R^t、R^u、R^v、R^w、R^xIt can be with R¹⁰、R¹¹Or R¹²It is bonded and forms ring.)

The meaning of " can be substituted with a substituent " the words in chemical structure that above-mentioned general formula (4)~(6) indicate with What is illustrated in above-mentioned general formula (1)~(3) is equivalent in meaning.

In the chemical structure that above-mentioned general formula (4)~(6) indicate, n is preferably 0~6 integer, more preferably 0~4 it is whole Number, particularly preferably 0~2 integer.It should be noted that the R for the chemical structure that above-mentioned general formula (4)~(6) indicate⁷And R⁸Bonding or R¹⁰、R¹¹、R¹²When being bonded and forming ring, n is preferably 1~8 integer, more preferably 1~7 integer, particularly preferably 1~3 Integer.

The chemistry that further preferred the following general formula of the chemical structure of the anion of salt (7), general formula (8) or general formula (9) indicate Structure.

(R¹³SO₂)(R¹⁴SO₂) N general formula (7)

(R¹³、R¹⁴It is each independently C_nH_aF_bCl_cBr_dI_e。

N, a, b, c, d, e are each independently 0 or more integer, meet 2n+1=a+b+c+d+e.

In addition, R¹³And R¹⁴It can be mutually bonded and form ring, at this point, meeting 2n=a+b+c+d+e.)

R¹⁵SO₃General formula (8)

(R¹⁵For C_nH_aF_bCl_cBr_dI_e。

N, a, b, c, d, e are each independently 0 or more integer, meet 2n+1=a+b+c+d+e.)

(R¹⁶SO₂)(R¹⁷SO₂)(R¹⁸SO₂) C general formula (9)

(R¹⁶、R¹⁷、R¹⁸It is each independently C_nH_aF_bCl_cBr_dI_e。

N, a, b, c, d, e are each independently 0 or more integer, meet 2n+1=a+b+c+d+e.

R¹⁶、R¹⁷、R¹⁸In wantonly two can be bonded and form ring, at this point, formed ring group meet 2n=a+b+c+d+e. In addition, R¹⁶、R¹⁷、R¹⁸Three can be bonded and form ring, at this point, two groups meet 2n=a+b+c+d+e in three, one Group meets 2n-1=a+b+c+d+e.)

In the chemical structure that above-mentioned general formula (7)~(9) indicate, n is preferably 0~6 integer, more preferably 0~4 it is whole Number, particularly preferably 0~2 integer.It should be noted that the R for the chemical structure that above-mentioned general formula (7)~(9) indicate¹³And R¹⁴Bonding Or R¹⁶、R¹⁷、R¹⁸When being bonded and forming ring, n is preferably 1~8 integer, more preferably 1~7 integer, particularly preferably 1~3 Integer.

In addition, a, c, d, e are preferably 0 in the chemical structure that above-mentioned general formula (7)~(9) indicate.

Metal salt is particularly preferably (CF₃SO₂)₂NLi (hereinafter sometimes referred to " LiTFSA "), (FSO₂)₂NLi is (below sometimes Referred to as " LiFSA "), (C₂F₅SO₂)₂NLi、FSO₂(CF₃SO₂)NLi、(SO₂CF₂CF₂SO₂)NLi、(SO₂CF₂CF₂CF₂SO₂)NLi、 FSO₂(CH₃SO₂)NLi、FSO₂(C₂F₅SO₂) NLi or FSO₂(C₂H₅SO₂)NLi.It should be noted that these metal salts are acid imide Salt.Particularly preferably use imide salts as metal salt accordingly it is also possible to say.

Metal salt uses the metal salt for being composed cation described above and anion with number appropriate respectively ?.Metal salt can also be can be used together a variety of using one of above-mentioned.

On the other hand, the metal salt in electrolyte (1) is to contain element sulphur and oxygen element in the chemical structure of anion Metal salt, metal salt cation it is identical as above-mentioned electrolyte of the invention.

The chemical structure of the anion of salt in electrolyte (1) contains element sulphur and oxygen element.Hereinafter, to the anion Chemical structure is specifically described.It should be noted that it is following only it is different from electrolyte (1) of the invention to electrolyte of the invention into Row explanation.Therefore, for the item being not particularly illustrated, electrolyte (1) is identical as electrolyte of the invention,

The chemical structure of the anion of salt is preferably the chemistry knot that above-mentioned general formula (1), general formula (2) or general formula (3) indicate Structure, but as follows for X¹~X⁵, with above-mentioned X¹~X⁵Compared to being further defined.

In electrolyte (1), the X of general formula (1)¹Selected from SO₂, S=O, X²Selected from SO₂, S=O.

In addition in electrolyte (1), the X of general formula (2)³Selected from SO₂, S=O.

In addition in electrolyte (1), the X of general formula (3)⁴Selected from SO₂, S=O, X⁵Selected from SO₂, S=O, X⁶Selected from SO₂, S=O.

The chemical structure of the anion of salt is more preferably the chemistry that above-mentioned general formula (4), general formula (5) or general formula (6) indicate Structure, but as follows for X⁷~X¹², with above-mentioned X⁷~X¹²Compared to being further defined.

In electrolyte (1), the X of general formula (4)⁷Selected from SO₂, S=O, X⁸Selected from SO₂, S=O.

In addition, in electrolyte (1), the X of general formula (5)⁹Selected from SO₂, S=O.

In addition, in electrolyte (1), the X of general formula (6)¹⁰Selected from SO₂, S=O, X¹¹Selected from SO₂, S=O, X¹²Selected from SO₂, S= O。

(organic solvent)

As the organic solvent with miscellaneous element, preferably miscellaneous element is having at least one in nitrogen, oxygen, sulphur, halogen Solvent, more preferable miscellaneous element are the organic solvent of at least one in nitrogen or oxygen.In addition, as having with miscellaneous element Solvent does not preferably have NH base, NH₂The non-protonic solvent for Protic Group such as base, OH base, SH base.

Particular instantiation has the organic solvent (hereinafter, sometimes referred to simply as " organic solvent ") of miscellaneous element, can enumerate acetonitrile, third The nitriles such as nitrile, acrylonitrile, malononitrile, 1,2- dimethoxy-ethane, 1,2- diethoxyethane, tetrahydrofuran, 1,2- bis- Alkane, 1,3- bis-Alkane, 1,4- bis-Alkane, 2,2- dimethyl -1,3- dioxolanes, 2- methyl oxinane, 2- methyl tetrahydro furan It mutters, the ethers such as crown ether, the carbonic esters such as ethylene carbonate, propylene carbonate, dimethyl carbonate, diethyl carbonate, methyl ethyl carbonate Class, the amides such as formamide, n,N-Dimethylformamide, n,N-dimethylacetamide, N-Methyl pyrrolidone, isopropyl isocyanide The isocyanates such as acid esters, n-propyl isocyanates, chloromethane based isocyanate, methyl acetate, ethyl acetate, propyl acetate, third The esters such as sour methyl esters, methyl formate, Ethyl formate, vinyl acetate, methyl acrylate, methyl methacrylate, glycidol The epoxies such as base methyl ether, epoxy butane, 2- ethyl ethylene oxide,Azoles, 2- ethylAzoles,Oxazoline, 2- methyl -2-Azoles Quinoline etc.Azole, the ketones such as acetone, methyl ethyl ketone, methyl iso-butyl ketone (MIBK), the acid anhydrides such as acetic anhydride, propionic andydride, dimethyl sulfone, ring fourth The sulfones class such as sulfone, the sulfoxide types such as dimethyl sulfoxide, the nitros class such as 1- nitropropane, 2- nitropropane, the furans such as furans, furfural, The ring-type esters such as gamma-butyrolacton, gamma-valerolactone, δ-valerolactone, the heteroaromatics class such as thiophene, pyridine, tetrahydro-pyrokomane, The heterocyclics such as 1- crassitude, N-methylmorpholine, the phosphoric acid esters such as trimethyl phosphate, triethyl phosphate.

In addition, the linear carbonate of the following general formula (10) expression can also be enumerated as the organic solvent with miscellaneous element.

R¹⁹OCOOR²⁰General formula (10)

(R¹⁹、R²⁰It is each independently selected from the C for chain-like alkyl_nH_aF_bCl_cBr_dI_eOr contain cyclic alkyl in chemical structure C_mH_fF_gCl_hBr_iI_jAny one of.N, a, b, c, d, e, m, f, g, h, i, j are each independently 0 or more integer, meet 2n+1=a+b+c+d+e, 2m=f+g+h+i+j.)

In the linear carbonate that above-mentioned general formula (10) indicates, n is preferably 1~6 integer, more preferably 1~4 integer, Particularly preferably 1~2 integer.M is preferably 3~8 integer, more preferably 4~7 integer, particularly preferably 5~6 it is whole Number.In addition, in the linear carbonate that above-mentioned general formula (10) indicates, particularly preferred dimethyl carbonate (hereinafter sometimes referred to " DMC "), Diethyl carbonate (hereinafter sometimes referred to " DEC "), methyl ethyl carbonate (hereinafter sometimes referred to " EMC ").

As the organic solvent with miscellaneous element, preferably relative dielectric constant is 20 or more or the ether oxygen with supply Solvent can enumerate the nitriles such as acetonitrile, propionitrile, acrylonitrile, malononitrile as such organic solvent, 1,2- dimethoxy-ethane, 1,2- diethoxyethane, tetrahydrofuran, 1,2- bis-Alkane, 1,3- bis-Alkane, 1,4- bis-Alkane, 2,2- dimethyl -1,3- The ethers such as dioxolanes, 2- methyl oxinane, 2- methyltetrahydrofuran, crown ether, n,N-Dimethylformamide, acetone, diformazan Base sulfoxide, sulfolane, particularly preferred acetonitrile (hereinafter sometimes referred to " AN "), 1,2- dimethoxy-ethane are (hereinafter sometimes referred to “DME”)。

These organic solvents can be used individually in electrolyte, also can be used together a variety of.

Electrolyte of the invention is characterized in that, in its vibrational spectrum, for the organic solvent contained by the electrolyte Peak intensity, the intensity at the original peak of organic solvent is set as Io, that the original peak of organic solvent is generated to the peak after displacement is (following When intensity sometimes referred to as " displacement peak ") is set as Is, meet Is > Io.That is, by electrolyte of the invention for vibrational spectrum In vibrational spectrum chart obtained by measurement, the relationship of above-mentioned 2 peak intensities is Is > Io.

Here, " the original peak of organic solvent " refers to the peak position when only carrying out vibrational spectrum measurement to organic solvent The peak that (wave number) is observed.The intensity Io value at the original peak of organic solvent and the intensity Is value at displacement peak are each in vibrational spectrum Height or area of the peak far from baseline.

In the vibrational spectrum of electrolyte of the invention, the original peak of organic solvent generates the peak after displacement, and there are multiple When, the peak based on the relationship for being easiest to judge Is and Io judges the relationship.In addition, electrolyte of the invention uses a variety of tools When having the organic solvent of miscellaneous element, selection is easiest to judge that (difference of Is and Io are most apparent) of the relationship of Is and Io is organic molten Agent judges the relationship of Is and Io based on its peak intensity.In addition, the displacement at peak is small, is displaced the overlap of peaks of front and back and takes a fancy to When going as gentle mountain, known means can be used and carry out peak separation, to determine the relationship of Is and Io.

It should be noted that being easiest in the vibrational spectrum of electrolyte for having used a variety of organic solvents with miscellaneous element Occur with the peak of the organic solvent (hereinafter sometimes referred to " preferred orientation solvent ") of cation coordination prior to other organic solvents Displacement.In the electrolyte for having used a variety of organic solvents with miscellaneous element, preferred orientation solvent is relative to miscellaneous element The quality % of organic solvent entirety be preferably 40% or more, more preferably 50% or more, further preferably 60% or more, it is special It You Xuanwei 80% or more.In addition, in the electrolyte for having used a variety of organic solvents with miscellaneous element, preferred orientation solvent Volume % relative to the organic solvent entirety with miscellaneous element is preferably 40% or more, and more preferably 50% or more, further Preferably 60% or more, particularly preferably 80% or more.

The relationship of above-mentioned 2 peak intensities in the vibrational spectrum of electrolyte of the invention preferably satisfies the item of 2 × Io of Is > Part more preferably meets the condition of 3 × Io of Is >, further preferably meets the condition of 5 × Io of Is >, particularly preferably meets Is > 7 The condition of × Io.The strong of the original peak of organic solvent is not observed in the vibrational spectrum of electrolyte of the invention most preferably Degree Io, the electrolyte for being displaced the intensity Is at peak is observed.Mean the whole of organic solvent contained by electrolyte in the electrolyte Molecule and the complete solvation of metal salt.Electrolyte most preferably of the invention is the whole point of organic solvent contained by electrolyte The state (state of Io=0) of son and the complete solvation of metal salt.

Infer in electrolyte of the invention, metal salt occurs with the organic solvent (or preferred orientation solvent) with miscellaneous element Interaction.Specifically, inferring the miscellaneous element of metal salt with the organic solvent (or preferred orientation solvent) with miscellaneous element Form coordinate bond, form be made of metal salt and the organic solvent with miscellaneous element (or preferred orientation solvent) it is stable Cluster compound (cluster).From the point of view of the result of aftermentioned embodiment, infer the cluster compound generally by 1 molecular metal salt Cooperate 2 molecules have miscellaneous element organic solvent (or preferred orientation solvent) and formed.Consider from this point, electrolysis of the invention The molar range relative to 1 mole of metal salt of the organic solvent (or preferred orientation solvent) with miscellaneous element in liquid is preferably 1.4 moles more than or lower than 3.5 moles, more preferably 1.5 moles~3.1 moles, further preferably 1.6 moles~3 moles.

Due to inferring in electrolyte of the invention, generally there is miscellaneous element by being coordinated 2 molecules to 1 molecular metal salt Organic solvent (or preferred orientation solvent) and form cluster compound, so the concentration (mol/L) of electrolyte of the invention depends on Density when metal salt and the respective molecular weight of organic solvent and formation solution.Therefore, by the concentration one of electrolyte of the invention It is unsuitable in general.

The concentration (mol/L) of electrolyte of the invention is illustrated respectively in table 1.

Table 1

Metal salt	Organic solvent	Concentration (mol/L)
			LiTFSA	DME	2.2~3.4
LiTFSA	AN	3.2~4.9
			LiFSA	DME	2.6~4.1
LiFSA	AN	3.9~6.0
			LiFSA	DMC	2.3~4.5
LiFSA	EMC	2.0~3.8
			LiFSA	DEC	1.8~3.6

Formed cluster compound organic solvent and from cluster compound formed unrelated organic solvent that environment is individually present is different.Cause This, vibrational spectrum measurement in, come the organic solvent of self-forming cluster compound peak be observed from observe come from and cluster compound shape It is displaced at the wave number at the peak (the original peak of organic solvent) of unrelated organic solvent to high wave number side or lower wave number side.That is, displacement Peak is equivalent to the peak to form the organic solvent of cluster compound.

As vibrational spectrum, IR spectrum or Raman spectrum can be enumerated.As the measuring method of IR measurement, nujol mull can be enumerated The transmission measurements method such as method, liquid-film method, the reflection measurements method such as ATR method.About selection IR spectrum or Raman spectrum, as long as choosing Select the spectrum that the relationship of Is and Io are easily determined in the vibrational spectrum of electrolyte of the invention.It should be noted that vibration light Spectrum measurement preferably carries out under conditions of can reduce or ignore the influence of the moisture in atmosphere.For example, it is preferable in hothouse, hand The low humidities such as casing carry out Raman without progress IR measurement under damp condition or in the state that electrolyte is put into closed container Measurement.

Here, to containing LiTFSA as metal salt and contain peak of the acetonitrile as the electrolyte of the invention of organic solvent It is specifically described.

When only carrying out IR measurement to acetonitrile, the peak of the stretching vibration of three keys between C and N usually 2100~ 2400cm^-1Nearby it is observed.

Here, it is based on existing common technical knowledge, it is assumed that LiTFSA is dissolved in acetonitrile solvent with the concentration of 1mol/L and is made The case where at electrolyte.Since acetonitrile 1L is equivalent to about 19mol, so there are the LiTFSA of 1mol in existing electrolyte 1L With the acetonitrile of 19mol.In this way, there is (being coordinated with Li) acetonitrile with LiTFSA solvation in existing electrolyte, existing simultaneously Largely not with (not with Li be coordinated) acetonitrile of LiTFSA solvation.However, for the molecule of acetonitrile with LiTFSA solvation and not For the molecule of acetonitrile of LiTFSA solvation, the environment as locating for molecule of acetonitrile is different, so observing in IR spectrum It has any different at the acetonitrile peak of the two.More specifically, not with the peak of the acetonitrile of LiTFSA solvation with only to acetonitrile carry out IR survey The same position of fixed situation (wave number) is observed, and on the other hand, it observes and the peak of the acetonitrile of LiTFSA solvation Peak position (wave number) is displaced to high wave number side.

Moreover, in the concentration of existing electrolyte, due to there are a large amount of not acetonitriles with LiTFSA solvation, so existing In the vibrational spectrum of some electrolyte, the intensity Io and acetonitrile at the original peak of acetonitrile original peak generates the intensity at the peak after displacement The relationship of Is is Is < Io.

On the other hand, electrolyte of the invention is compared with existing electrolyte, and the concentration of LiTFSA is high, and in electrolyte It is more than the molecule of acetonitrile number not with LiTFSA solvation with (forming cluster compound) molecule of acetonitrile number of LiTFSA solvation.Then, The intensity Io and acetonitrile at peak in the vibrational spectrum of electrolyte of the invention, acetonitrile is original original peak generates the peak after displacement The relationship of intensity Is be Is > Io.

The organic solvent for thinking useful to Io and Is in the vibrational spectrum for calculating electrolyte of the invention is instantiated in table 2 Wave number and its ownership.It should be noted that further including being observed because the measurement device, determination of the environment, determination condition of vibrational spectrum are different Peak sometimes different from the wave number below situation of wave number.

Table 2

Organic solvent	Wave number (cm^-1)	Ownership
			Ethylene carbonate	1769	Double bond between C and O
Propylene carbonate	1829	Double bond between C and O
			Acetic anhydride	1785、1826	Double bond between C and O
Acetone	1727	Double bond between C and O
			Acetonitrile	2285	Three keys between C and N
Acetonitrile	899	C -- C single bond
			DME	1099	C-O singly-bound
DME	1124	C-O singly-bound
			N,N-Dimethylformamide	1708	Double bond between C and O
Gamma-butyrolacton	1800	Double bond between C and O
			Nitropropane	1563	Double bond between N and O
Pyridine	977	It is unknown
			Dimethyl sulfoxide	1017	S-O key

It, can be using well known data as reference for the wave number and its ownership of organic solvent.As a reference, it can lift Japanese serial 17 Raman spectroscopies of spectroscopy meeting measuring method out, the macro husband in shore mouthful, level land dawn, association publishing centre, 231~249 Page.In addition, can also predict to think the wave number for calculating useful organic solvent to Io and Is by using the calculating of computer Wave number when being coordinated with organic solvent and metal salt is displaced.It is, for example, possible to use Gaussian09 (registered trademark, Gaussian Company), Density functional is set as B3LYP, basis function is set as 6-311G++ (d, p) to calculate.Those skilled in the art can With the record of reference table 2, well known data, the calculated result of computer, the peak of organic solvent is selected, calculates Io and Is.

Electrolyte of the invention compared with existing electrolyte, metal salt and organic solvent there are environment differences, and Metal salt concentrations are high, therefore can expect to improve the metal ion conveying speed in electrolyte and (when especially metal is lithium, improve Lithium delivery rate), the reaction speed that improves electrode and electrolyte interface, mitigate caused electrolysis when the high power charging-discharging of battery Unevenness, increase electric double layer capacity of the salinity of liquid etc..As described below, it is believed that at least part of these excellent effects be by The SEI envelope bring of the special construction of cathode and/or positive electrode surface is formed in from electrolyte of the invention.Furthermore, it is believed that By the cooperation of the SEI envelope and electrolyte of the invention of the special construction, above-mentioned various excellent effects can be played, for example, Improve the reaction speed between electrode and electrolyte interface.In addition, in electrolyte of the invention, due to the organic of miscellaneous element The major part and metal salt of solvent form cluster compound, so the vapour pressure of organic solvent contained by electrolyte is lower.As it As a result, it is possible to reduce organic solvent from the volatilization in electrolyte of the invention.

The manufacturing method of electrolyte of the invention is illustrated.Electrolyte of the invention is compared with existing electrolyte Compared with the content of metal salt is more, therefore is coagulated in the manufacturing method for adding organic solvent into the metal salt of solid (powder) Polymers, it is difficult to manufacture the electrolyte of solution state.Therefore, in the manufacturing method of electrolyte of the invention, preferably to organic solvent In be slowly added metal salt, and manufactured when maintaining the solution state of electrolyte.

According to the type of metal salt and organic solvent, electrolyte of the invention includes metal salt to be more than to know all the time The mode of saturation solubility be dissolved in the liquid of organic solvent.The manufacturing method of such electrolyte of the invention includes will have There are organic solvent and the metal salt mixing of miscellaneous element, makes dissolving metal salts, prepare the 1st dissolution process of the 1st electrolyte；It is stirring And/or under the conditions of heating, above-mentioned metal salt is added in the 1st electrolyte of Xiang Shangshu, makes above-mentioned dissolving metal salts, prepares hypersaturated state The 2nd electrolyte the 2nd dissolution process；Under the conditions of stirring and/or heating, above-mentioned metal salt is added in the 2nd electrolyte of Xiang Shangshu, Make above-mentioned dissolving metal salts, prepares the 3rd dissolution process of the 3rd electrolyte.

Here, above-mentioned " hypersaturated state " refers to the case where relieving stirring and/or heating condition or imparts vibration In the case that equal nucleus generate energy, state that metal salt crystals are precipitated from electrolyte.2nd electrolyte is " hypersaturated state ", 1st electrolyte and the 3rd electrolyte are not " hypersaturated states ".

In other words, the above-mentioned manufacturing method of electrolyte of the invention is passed through includes in thermodynamically stable liquid condition Then 1st electrolyte of existing metal salt concentrations becomes heat via the 2nd electrolyte of the liquid condition of thermodynamic instability 3rd electrolyte of the stable new liquid condition of mechanics, i.e., electrolyte of the invention.

3rd electrolyte of stable liquid condition keeps liquid condition under typical conditions, so inferring in the 3rd electrolysis In liquid, for example, by being that 2 molecule organic solvents are constituted, steady by these intermolecular strong coordinate bonds relative to 1 molecule lithium salts Surely the cluster compound changed hinders the crystallization of lithium salts.

1st dissolution process is that will have heteroatomic organic solvent and metal salt mixing, makes dissolving metal salts, preparation the 1st The process of electrolyte.

In order to have heteroatomic organic solvent and metal salt mixing, can add in heteroatomic organic solvent Enter metal salt, can also be added into metal salt has heteroatomic organic solvent.

1st dissolution process preferably carries out under the conditions of stirring and/or heating.As long as mixing speed is suitably set. Heating condition is preferably suitably controlled with thermostats such as water-bath or oil baths.Due to metal salt dissolution when generate heat of solution, so When using metal salt by thermally labile, temperature condition is preferably strictly controlled.Furthermore it is possible to organic solvent is pre-cooled, The 1st dissolution process can be carried out in the cooling condition.

1st dissolution process and the 2nd dissolution process can continuously be implemented, can also be with the 1st dissolution process of temporary safe-keeping (standing) Obtained in the 1st electrolyte implement the 2nd dissolution process by after a certain period of time.

2nd dissolution process is that metal salt is added into the 1st electrolyte under the conditions of stirring and/or heating, keeps metal salt molten Solution, the process for preparing the 2nd electrolyte of hypersaturated state.

Since the 2nd dissolution process is the 2nd electrolyte for preparing the hypersaturated state of thermodynamic instability, so must stir It is carried out under the conditions of mixing and/or heating.Can by with mixer etc. with blender agitating device carry out the 2nd dissolution process and Under stirring condition, or the 2nd dissolution can be carried out by using stirrer and the device (blender) for making stirrer work Process and under the stirring condition.Heating condition is preferably suitably controlled with thermostats such as water-bath or oil baths.Certainly, particularly preferably The 2nd dissolution process is carried out using the device or system for having both agitating function and heating function.It should be noted that heating described herein Refer to the temperature that object is heated up to room temperature (25 DEG C) or more.Warm temperature is more preferably 30 DEG C or more, further preferably 35 DEG C or more.Additionally, it is preferred that warm temperature is the temperature of the low boiling point than organic solvent.

In 2nd dissolution process, in the case that the metal salt of addition is without sufficiently dissolving, implement mixing speed increase and/ Or further heating.At this point it is possible to which be added to the electrolyte of the 2nd dissolution process has heteroatomic organic solvent on a small quantity.

The crystal of metal salt is precipitated if temporarily standing the 2nd electrolyte obtained in the 2nd dissolution process, therefore preferably It is continuous to implement the 2nd dissolution process and the 3rd dissolution process.

3rd dissolution process is that metal salt is added into the 2nd electrolyte under the conditions of stirring and/or heating, keeps metal salt molten Solution, the process for preparing the 3rd electrolyte.In 3rd dissolution process, due to needing that gold is added into the 2nd electrolyte of hypersaturated state Belong to salt and dissolve, so must be carried out under the conditions of stirring and/or heating in the same manner as the 2nd dissolution process.Specific stirring and/ Or heating condition is same as the condition of the 2nd dissolution process.

If passing through organic solvent and metal salt added by the 1st dissolution process, the 2nd dissolution process and the 3rd dissolution process Molar ratio generally 2:1 or so, then the manufacture of the 3rd electrolyte (electrolyte of the invention) terminates.Even if release stirring and/or Heating condition, metal salt crystals will not be precipitated from electrolyte of the invention.From the point of view of these situations, electrolysis of the invention is inferred Liquid form for example by relative to 1 molecule of lithium salts be it is that 2 molecule of organic solvent is constituted, by these intermolecular strong coordinate bonds and Stabilized cluster compound.

It should be noted that when manufacturing electrolyte of the invention, according to the type of metal salt and organic solvent, in each dissolution work Under treatment temperature in sequence, even if in the case where not via above-mentioned hypersaturated state, using institute in above-mentioned 1st~3 dissolution process The specific dissolution means stated also can suitably manufacture electrolyte of the invention.

In addition, in the method for manufacturing electrolyte of the invention preferably there is the electrolyte to manufacture midway to vibrate Spectrometric vibrational spectrum mensuration operation.As specific vibrational spectrum mensuration operation, for example, it may be sampling a part system Each electrolyte of midway is made for vibrational spectrum method for measuring, is also possible in situ (on the scene) shake to each electrolyte Move spectrometric method.As vibrational spectrum method for measuring is carried out to electrolyte in situ, can enumerate to transparent flowing Pond imports the electrolyte of manufacture midway the method that measures vibrational spectrum, or using transparent manufacture container outside the container into Row Raman method for measuring.

Manufacturing method by making electrolyte of the invention includes vibrational spectrum mensuration operation, can be confirmed on the way during manufacturing The relationship of Is and Io in electrolyte, therefore can judge whether the electrolyte for manufacturing midway becomes electrolyte of the invention, separately Outside, when the electrolyte on way does not become electrolyte of the invention during manufacturing, the additional metal salt ability how much measured can be held Electrolyte is set to become electrolyte of the invention.

In electrolyte of the invention, except it is above-mentioned with the organic solvent of miscellaneous element in addition to, low polarity (low Jie can also be added Electric constant) or it is low supply number, the solvent particularly to interact is not shown with metal salt, that is, in electrolyte of the present invention The formation and maintenance of above-mentioned cluster compound do not have influential solvent.By the way that such solvent is added in electrolyte of the invention, It can expect the effect that the viscosity of electrolyte is reduced in the state of keeping the formation of above-mentioned cluster compound of electrolyte of the invention.

As the solvent particularly to interact is not shown with metal salt, specifically, benzene, toluene, ethylbenzene, neighbour can be illustrated Dimethylbenzene, meta-xylene, paraxylene, 1- methyl naphthalene, hexane, heptane, hexamethylene.

In addition, in electrolyte of the invention, except it is above-mentioned with the organic solvent of miscellaneous element in addition to, anti-flammability can also be added Solvent.By the way that the solvent of anti-flammability to be added in electrolyte of the invention, electrolyte of the invention can be further increased Degree of safety.As the solvent of anti-flammability, the halogen-based solvents such as carbon tetrachloride, tetrachloroethanes, hydrofluoroether, tripotassium phosphate can be illustrated The phosphoric acid derivatives such as ester, triethyl phosphate.

In addition, if electrolyte of the invention is mixed with polymer, inorganic filler and forms mixture, then the mixture Enclosed electrolyte, becomes quasi- solid electrolyte.Electrolyte by using quasi- solid electrolyte as battery, is able to suppress battery In electrolyte leakage.

As above-mentioned polymer, can gather using used in the non-aqueous electrolyte secondary batteries such as lithium ion secondary battery Close the polymer of object, common chemical crosslinking.The absorbable electrolyte such as particularly preferred Kynoar, polyhexafluoropropylene become solidifying The polymer of gelatinization, polyethylene oxide etc. have imported the polymer of ionic conductivity group to polymer.

As specific polymer, polymethyl acrylate, polymethyl methacrylate, polyethylene oxide, polycyclic can be illustrated Ethylene Oxide, polyacrylonitrile, Kynoar, polyethylene glycol dimethacrylate, polyethylene glycol acrylate, poly epihydric alcohol (Polyglycidol), polytetrafluoroethylene (PTFE), polyhexafluoropropylene, polysiloxanes, polyvinyl acetate, polyvinyl alcohol, polyacrylic acid, The polycarboxylic acids such as polymethylacrylic acid, poly- itaconic acid, poly- fumaric acid, poly- crotonic acid, poly- angelic acid, carboxymethyl cellulose, styrene- The unsaturation that butadiene rubber, nitrile-butadiene rubber, polystyrene, polycarbonate, maleic anhydride and di-alcohols are copolymerized into is poly- Ester, the polyethylene oxide derivant with substituent group, vinylidene and hexafluoropropene copolymer.In addition, as above-mentioned polymerization Object can choose copolymer made of making to constitute two kinds or more of the monomer copolymerization of above-mentioned specific polymer.

As above-mentioned polymer, further preferably polysaccharide.As specific polysaccharide, glycogen, cellulose, crust can be illustrated Matter, agarose, carragheen, heparin, hyaluronic acid, pectin, amylopectin, xyloglucan, amylose.Furthermore it is possible to using The material for containing these polysaccharides can illustrate the agar containing polysaccharides such as agaroses as the material as above-mentioned polymer.

As above-mentioned inorganic filler, the inorganic ceramics such as preferred oxides, nitride.

Inorganic ceramic has hydrophily and hydrophobic functional group on its surface.Therefore, the functional group is by attracting electrolysis Liquid can form conductive vias in inorganic ceramic.Also, the inorganic ceramic dispersed in electrolyte is formed using above-mentioned functional group The network that inorganic ceramic is linked to be each other can play the effect of enclosed electrolyte.Utilize such function of inorganic ceramic, Neng Gougeng Properly inhibit the leakage of the electrolyte in battery.In order to properly play the above-mentioned function of inorganic ceramic, inorganic ceramic is preferred For shape of particle, its particularly preferred partial size is nanometer level.

As the type of inorganic ceramic, general aluminium oxide, silica, titanium oxide, zirconium oxide, phosphoric acid lithium salts can be enumerated Deng.In addition, inorganic ceramic itself can have lithium conductibility, specifically, Li can be illustrated₃N、LiI、LiI-Li₃N-LiOH、 LiI-Li₂S-P₂O₅、LiI-Li₂S-P₂S₅、LiI-Li₂S-B₂S₃、Li₂O-B₂S₃、Li₂O-V₂O₃-SiO₂、Li₂O-B₂O₃-P₂O₅、 Li₂O-B₂O₃-ZnO、Li₂O-Al₂O₃-TiO₂-SiO₂-P₂O₅、LiTi₂(PO₄)₃、Li-βAl₂O₃、LiTaO₃。

It can be using glass ceramics as inorganic filler.Glass ceramics can enclose ionic liquid, so to the present invention Electrolyte also it can be expected that same effect.As glass ceramics, xLi can be illustrated₂S-(1-x)P₂S₅The compound of expression and general A part of the S of compound compound obtained by other elements substitutions and by a part germanium of the P of the compound Compound obtained by substitution.

Density d (the g/cm of electrolyte of the invention³) it is preferably d >=1.2 or d≤2.2, more preferably 1.2≤d≤2.2 In the range of, it is especially excellent further preferably in the range of 1.26≤d≤1.8 more preferably in the range of 1.24≤d≤2.0 It is selected as in the range of 1.27≤d≤1.6.It should be noted that density d (the g/cm of electrolyte of the invention³) refer to it is close at 20 DEG C Degree.D/c described below is with above-mentioned d divided by value obtained by salinity c (mol/L).

The d/c of electrolyte of the invention is 0.15≤d/c≤0.71, preferably in the range of 0.15≤d/c≤0.56, more Preferably in the range of 0.25≤d/c≤0.56, further preferably in the range of 0.26≤d/c≤0.50, particularly preferably In the range of 0.27≤d/c≤0.47.

The d/c of electrolyte of the invention also can specify that in the case where special metal salt and organic solvent.For example, selection LiTFSA is as metal salt, more excellent in the range of d/c is preferably 0.42≤d/c≤0.56 when selecting DME as organic solvent It is selected as in the range of 0.44≤d/c≤0.52.Select LiTFSA as metal salt, when selecting AN as organic solvent, d/c is preferred In the range of 0.35≤d/c≤0.41, more preferably in the range of 0.36≤d/c≤0.39.Select LiFSA as metal Salt, when selecting DME as organic solvent, in the range of d/c is preferably 0.32≤d/c≤0.46, more preferably 0.34≤d/c≤ In the range of 0.42.Select LiFSA as metal salt, when selecting AN as organic solvent, d/c be preferably 0.25≤d/c≤ In the range of 0.48, the more preferably range of 0.25≤d/c≤0.38, the further preferably range of 0.25≤d/c≤0.31 It is interior, further preferably in the range of 0.26≤d/c≤0.29.It selects LiFSA as metal salt, selects DMC as organic molten When agent, in the range of d/c is preferably 0.32≤d/c≤0.46, more preferably in the range of 0.34≤d/c≤0.42.Selection LiFSA is as metal salt, when selecting EMC as organic solvent, in the range of d/c is preferably 0.34≤d/c≤0.50, more preferably In the range of 0.37≤d/c≤0.45.Select LiFSA as metal salt, when selecting DEC as organic solvent, d/c is preferably In the range of 0.36≤d/c≤0.54, more preferably in the range of 0.39≤d/c≤0.48.

For electrolyte of the invention compared with existing electrolyte, metal salt and organic solvent are close there are environment difference Degree is high, therefore can expect to improve the metal ion conveying speed in electrolyte and (when especially metal is lithium, improve lithium conveying speed Rate), the reaction speed of electrode and electrolyte interface is improved, the salt for mitigating caused electrolyte when the high power charging-discharging of battery is dense The unevenness of degree increases electric double layer capacity etc..In addition, in electrolyte of the invention, due to density height, so having contained by electrolyte The vapour pressure of solvent is lower.As a result, it is possible to reduce the volatilization of organic solvent from electrolyte of the invention.

In addition, the viscosity of such electrolyte of the invention is higher than the viscosity of existing electrolyte.Therefore, if it is using The non-aqueous electrolyte secondary battery of the invention of electrolyte of the invention even if battery is damaged can also inhibit electrolyte to leak. In addition, it is obvious to have used the non-aqueous electrolyte secondary battery of existing electrolyte capacity in high speed charge and discharge cycles to reduce.Make For one of its reason, it is believed that the Li density unevenness generated in electrolyte when being due to quick repeated charge, cause with electricity The reaction interface electrolyte of pole can not supply the Li of sufficient amount, that is to say, that the Li density unevenness of electrolyte.However, of the invention Electrolyte metal concentration it is higher for existing electrolyte.Such as the preferred Li concentration of electrolyte of the invention It is 2~5 times or so of the Li concentration of general electrolyte.Think to contain in the electrolyte of the invention of Li with high concentration in this way, The uneven of Li is reduced, as a result, thinking that capacity when inhibiting high speed charge and discharge cycles reduces.Additionally, it is believed that due to the present invention Electrolyte be high viscosity, so the liquid retention of the electrolyte of electrode interface improves, inhibition is in electrode interface insufficient electrolyte State (the so-called withered state of liquid) is also the reason that capacity when inhibiting high speed charge and discharge cycles reduces.

If the viscosities il (mPas) to electrolyte of the invention is illustrated, the preferably range of 10 < η < 500, more The preferably range of 12 < η < 400, the further preferably range of 15 < η < 300, the particularly preferably model of 18 < η < 150 It encloses, most preferably the range of 20 < η < 140.

In addition, the ionic conductivity σ (mS/cm) of electrolyte is higher, the ion the easy to move in the electrolytic solution.Therefore, this The electrolyte of sample can become the electrolyte of excellent battery.If the ionic conductivity σ (mS/cm) to electrolyte of the invention is carried out Illustrate, then preferably 1≤σ.For the ionic conductivity σ (mS/ of the electrolyte in non-aqueous electrolyte secondary battery of the invention Cm), if the preferred range comprising the upper limit have to be illustrated, the preferably range of 2 < σ < 200, more preferably 3 < σ < 100 Range, the further preferably range of 4 < σ < 50, the particularly preferably range of 5 < σ < 35.

However, foring in the cathode of non-aqueous electrolyte secondary battery (1) of the invention and/or the surface of anode containing S, O Envelope.In most cases, it also forms on the surface of the cathode of non-aqueous electrolyte secondary battery (2) and/or anode containing S, O quilt Film.As described below, which contains S and O, at least has S=O structure.Moreover, because this, which contains S, O envelope, has S=O structure, It is believed that being from electrolyte.Think in electrolyte of the invention, compared with common electrolyte, Li cation and yin Ion is closer from obtaining.Therefore anion is preferentially reduced decomposition by force by the electrostatic influence from Li cation.Using one As electrolyte general non-aqueous electrolyte secondary battery in, (such as the EC: ethylene carbonate of organic solvent contained by electrolyte Deng) it is reduced decomposition, SEI envelope is constituted by the decomposition product of the organic solvent.But non-aqueous solution electrolysis of the invention as described above Anion is preferentially reduced decomposition in electrolyte of the invention contained by electrolitc secondary cell.It is therefore contemplated that non-water power of the invention SEI envelope in solution electrolitc secondary cell is that the envelope containing S, O contains the largely S=O structure from anion.That is, making With in the common non-aqueous electrolyte secondary battery of common electrolyte, the SEI quilt of the decomposition product from organic solvents such as EC Film is fixed on electrode surface.On the other hand, in the non-aqueous electrolyte secondary battery of the invention for having used electrolyte of the invention In, the SEI envelope of the mainly anion from metal salt is fixed on electrode surface.

Though the envelope containing S, O in non-aqueous electrolyte secondary battery of the invention is with charge and discharge in addition, reason is still uncertain Electric generating state variation.For example, as described below, the ratio of the elements such as thickness, S, O according to the state of charge and discharge containing S, O envelope Sometimes change.It is therefore contemplated that non-aqueous electrolyte secondary battery of the invention containing in S, O envelope exist from above-mentioned anion Decomposition product, the portion part being fixed in envelope (hereinafter, being known as fixed part as needed) and reversibly increased and decreased with charge and discharge Divide (hereinafter, being known as adsorption section as needed).And speculate adsorption section have with fixed part in the same manner as from metal salt it is negative from The structures such as the S=O of son.

It should be explained that, it is believed that it is made of containing S, O envelope the decomposition product of electrolyte, in addition contains adsorbate, therefore, it is considered that containing S, the major part (or whole) of O envelope is generated after the first charge and discharge of non-aqueous electrolyte secondary battery.That is, Non-aqueous electrolyte secondary battery of the invention has the envelope containing S, O on the surface of cathode and/or the surface of anode when in use.Contain S, other constituents sulphur according to contained by electrolyte of O envelope and the ingredient other than oxygen, the composition of cathode etc. are had nothing in common with each other. As long as content ratio is not particularly limited in addition, this contains S, O envelope containing S=O structure.In addition, the institute containing S, O envelope Ingredient and amount other than the S=O structure contained are not particularly limited.Moreover, can only be formed in negative terminal surface containing S, O envelope, It can only be formed in positive electrode surface.However, thinking that the envelope containing S, O is the metal contained by the electrolyte of the invention as described above The anion of salt, therefore the ingredient for being preferred from the anion of the metal salt is more than what other ingredients contained.Additionally, it is preferred that containing S, O envelope is formed in negative terminal surface and positive electrode surface.Hereinafter, as needed, the envelope containing S, O formed on the surface of cathode is claimed For cathode envelope containing S, O, it is known as the positive envelope containing S, O containing S, O envelope for what is formed on the surface of anode.

As described above, preferably using imide salts as the metal salt in electrolyte of the invention.All the time, Know the technology that imide salts are added in oriented electrolyte, it is known that in the non-aqueous electrolyte secondary battery for having used this electrolyte In, the envelope on anode and/or cathode is in addition to the compound containing the organic solvent decomposition product from electrolyte, also containing next It is the compound containing S from the compound of imide salts.Such as in Japanese Unexamined Patent Publication 2013-145732, describes and contained using the envelope Ingredient of some a part from imide salts can inhibit the increase of the internal resistance of non-aqueous electrolyte secondary battery, and energy Improve the durability of non-aqueous electrolyte secondary battery.

However, it is above-mentioned in the prior art, since the ingredient from imide salts in following reason envelope can not be dense Change.Firstly, reacting, making non-aqueous in order to make graphite that invertibity occur with charge carrier when using graphite as negative electrode active material Electrolyte secondary battery reversibly carries out charge and discharge, it is believed that needs to form SEI envelope on the surface of cathode.In the past, in order to be formed The SEI envelope uses the organic solvent using EC as the cyclic carbonate compound of representative as electrolyte.Moreover, using should The decomposition product of cyclic carbonate compound forms SEI envelope.That is, the existing electrolyte containing imide salts contains greatly Measure the cyclic carbonates such as the EC as organic solvent and containing the imide salts as additive.But at this point, SEI envelope Principal component is the ingredient from organic solvent, it is difficult to increase the content of the imide salts of SEI envelope.

In addition, it is desirable to by imide salts not as additive and as metal salt (that is electrolytic salt, support salt) In use, the combination with the collector of anode must be taken into consideration.That is, it is known that imide salts corrosion is used usually as anode The aluminium collector that collector uses.When therefore, especially with the anode of the current potential work with 4V or so, need to make with aluminium shape At the LiPF of passivation₆It is coexisted Deng the electrolyte for electrolytic salt with aluminium collector.In addition, in existing electrolyte, from from From the viewpoint of sub- conductivity, viscosity, by LiPF₆, the electrolytic salt of compositions such as imide salts total concentration most preferably 1mol/ L~2mol/L or so (Japanese Unexamined Patent Publication 2013-145732).So if the LiPF of addition sufficient amount₆, then the addition of imide salts Amount is necessarily reduced, so there is the metal salt for being difficult to largely use imide salts as electrolyte.Hereinafter, according to need It wants, imide salts is referred to as metal salt sometimes.

In contrast, electrolyte of the invention contains metal salt with high concentration.Moreover, as described below, it is believed that of the invention Metal salt with previous entirely different state in electrolyte to exist.Therefore, electrolyte of the invention and existing electrolyte is not Together, it is less prone to and is led to the problem of because metal salt is high concentration.For example, being able to suppress using electrolyte of the invention by electricity The viscosity for solving liquid rises the input and output reduced performance of caused non-aqueous electrolyte secondary battery, additionally it is possible to inhibit aluminium collector Corrosion.In addition, the metal salt that electrolyte is contained with high concentration is preferentially reduced decomposition on cathode.Even if as a result, not using The cyclic carbonate compounds such as the EC as organic solvent can also form the SEI of the special construction from metal salt on cathode Envelope, the i.e. envelope containing S, O.Therefore non-aqueous electrolyte secondary battery of the invention is even with graphite as negative electrode active material When, also charge and discharge can be reversibly carried out in the case where organic solvent does not use cyclic carbonate compound.

Therefore non-aqueous electrolyte secondary battery of the invention as negative electrode active material and uses aluminium collection even with graphite It, also can be without using as the cyclic carbonate compound of organic solvent or as gold when electric body uses collector as anode Belong to the LiPF of salt₆In the case where reversibly carry out charge and discharge.And the big of the SEI envelope of cathode and/or positive electrode surface can be made Part is made of the ingredient from anion.As described below, can improve containing S, O envelope containing the ingredient from anion is utilized The battery behavior of non-aqueous electrolyte secondary battery.

It should be noted that having used the envelope of cathode in the non-aqueous electrolyte secondary battery of the general electrolyte containing EC solvent Polymer architecture made of being closed containing the carbon poly largely from EC solvent.In contrast, the secondary electricity of nonaqueous electrolyte of the invention Cathode in pond almost (or complete) is free of polymer architecture made of such carbon poly is closed containing S, O envelope, and containing a large amount of next From the structure of the anion of metal salt.Positive envelope is also same.

However, electrolyte of the invention contains the cation of metal salt with high concentration.Therefore, in electrolyte of the invention, Distance between adjacent cation is extremely close.Moreover, the cation such as lithium ion exists in the charge and discharge of non-aqueous electrolyte secondary battery When moving between positive electrode and negative electrode, nearest cation is supplied to the electrode first with the electrode of mobile target.Then, in quilt The place that the cation of supply existed, the others cation adjacent with the cation are mobile.That is, expecting this hair In bright electrolyte, adjacent cation is generated towards the electrode as supply object and successively singly changes position in this way The phenomenon as dominoes.It is therefore contemplated that when charge and discharge cation moving distance it is short, only in this way cation Movement speed is just high.Moreover, thus, it is believed that have the anti-of the non-aqueous electrolyte secondary battery of the invention of electrolyte of the invention Answer speed height.Additionally, it is believed that the electrode (that is cathode and/or anode) of non-aqueous electrolyte secondary battery of the invention has Containing S, O envelope, this contains S, O envelope with S=O structure and containing a large amount of cation.Think this containing sun contained by S, O envelope from It is sub to be preferentially fed into electrode.It is therefore contemplated that in non-aqueous electrolyte secondary battery of the invention, it is abundant due to having near electrode Cationic source (that is envelope containing S, O) and further increase cation conveying speed.It is therefore contemplated that of the invention is non- In Water-Electrolyte secondary cell, electrolyte through the invention and the cooperation containing S, O envelope play excellent battery behavior.

It is only limitted to refer to, it is believed that the SEI envelope of cathode is electrolyte reduction decomposition in the case where providing voltage below, by this time What the deposit of the electrolyte of generation was constituted.That is, in order to which the surface in cathode efficiently produces the above-mentioned envelope containing S, O, It is preferred that it is following so that the minimum value of the current potential of the cathode of non-aqueous electrolyte secondary battery of the invention is reached regulation.Specifically, this Minimum value of the non-aqueous electrolyte secondary battery of invention when to electrode is lithium preferably in the current potential of cathode is 1.3V below Under the conditions of the battery that uses.

Cathode in non-aqueous electrolyte secondary battery of the invention is not particularly limited.As negative electrode active material, can make With the general negative electrode active material that can occlude and release charge carrier.For example, non-aqueous electrolyte secondary battery is lithium ion two When primary cell, as negative electrode active material, as long as selection can occlude and release the material of lithium ion.More specifically, may be used Think the element (simple substance) that alloying can occur with Li et al. charge carrier, the alloy containing the element or containing the chemical combination of the element Object.Specifically, the 14th race such as Li, carbon, silicon, germanium, tin member can be respectively adopted in the form of simple substance as negative electrode active material Element, the 13rd race's element such as aluminium, indium, the 12nd race's element such as zinc, cadmium, the 15th race's element such as antimony, bismuth, the alkaline-earth metal such as magnesium, calcium, silver, 11st race's elements such as gold.If negative electrode active material is using silicon etc., since 1 silicon atom is reacted with multiple lithiums, so being high The active material of capacity, but significantly asked due to being likely to occur the occlusion with lithium and releasing the expansion of the volume generated and shrink Topic, so in order to reduce this possibility, further preferably using the simple substance and transition metal etc. such as silicon others element combinations at conjunction Gold or compound are as negative electrode active material.As alloy or the concrete example of compound, Ag-Sn alloy can be enumerated, Cu-Sn is closed The tin based materials such as gold, Co-Sn alloy, the carbon-based materials such as various graphite are disproportionated into the SiO of elementary silicon and silica_x(0.3≤x ≤ 1.6) complex that the silicon systems material such as, elementary silicon or silicon systems material and carbon-based material are combined into.In addition, as negative electrode active material Matter can also use Nb₂O₅、TiO₂、Li₄Ti₅O₁₂、WO₂、MoO₂、Fe₂O₃Equal oxides or Li_3-xM_xN (M=Co, Ni, Cu) table The nitride shown.As negative electrode active material, these substances more than one can be used.

As described above, non-aqueous electrolyte secondary battery (1) of the invention is formd in negative terminal surface containing S, O envelope.Therefore, Cope with low potential cathode.Specifically, the objects containing carbon such as graphite may be selected in non-aqueous electrolyte secondary battery (1) Matter, Si system negative electrode active material as negative electrode active material.Graphite can be natural graphite, artificial graphite, and partial size does not have yet It is particularly limited to.

Non-aqueous electrolyte secondary battery of the invention has: having the cathode that can occlude and release lithium ion electrical charge carrier The cathode of active material；Anode with the positive active material that can occlude and release the charge carrier；With the above-mentioned present invention Electrolyte.For example, negative electrode active material mass-energy occludes when non-aqueous electrolyte secondary battery of the invention is lithium ion secondary battery With releasing lithium ion, positive electrode active material mass-energy occludes and releases lithium ion, and electrolyte is using lithium salts as metal salt.

Cathode has collector and is bonded in the negative electrode active material layer on the surface of collector.About negative electrode active material, It has described.

Collector refers to for continuing circulating current to electrode in the electric discharge or charging of non-aqueous electrolyte secondary battery The electronics high conduction body of chemical stabilization.As the collector of cathode, can illustrate selected from silver, copper, gold, aluminium, tungsten, cobalt, zinc, At least one of nickel, iron, platinum, tin, indium, titanium, ruthenium, tantalum, chromium, molybdenum and stainless steel and other metal materials.Collector can use public affairs The protective layer known is coating.The collector of using known method to handle on the surface of collector can be used as collector.

Collector can be using the forms such as paillon, thin slice, film, threadiness, rodlike, net.Therefore, as collector, for example, can It is preferable to use the metal foils such as copper foil, nickel foil, aluminium foil, stainless steel foil.When collector is the form of paillon, thin slice, film, thickness is excellent It is selected as in the range of 1 μm~100 μm.

Negative electrode active material layer includes negative electrode active material and binder and/or conductive auxiliary agent as needed.It is non-aqueous Electrolyte secondary battery (2) uses specific binder.

Binder, which plays, to be made between negative electrode active material particle or negative electrode active material and conductive auxiliary agent are fixed on current collection The effect on the surface of body.The binder of non-aqueous electrolyte secondary battery (2) contains the polymer with hydrophilic radical.As having The hydrophilic radical of the polymer of hydrophilic radical can illustrate the phosphorus such as carboxyl, sulfo group, silanol group, amino, hydroxyl, amino, phosphate The group etc. of acid system.Wherein, preferably contain in the molecules such as polyacrylic acid (PAA), carboxymethyl cellulose (CMC), polymethylacrylic acid There are the polymer or the polymer containing sulfo group such as poly- (p styrene sulfonic acid) of carboxyl.

The polymer containing a large amount of carboxyls and/or sulfo group such as copolymer of polyacrylic acid or acrylic acid and vinyl sulfonic acid For water solubility.Therefore the polymer with hydrophilic radical is preferably water-soluble polymer, and multiple carboxylics are contained in a preferably molecule The polymer of base and/or sulfo group.

Polymer in molecule containing carboxyl for example can be with the method for polymerizeing the acid monomers such as polyacrylic acid or to carboxylic The polymer such as methylcellulose (CMC) assign the methods of method of carboxyl to manufacture.It, can exemplary propylene acid, first as acid monomers Acid with a carboxyl in the molecules such as base acrylic acid, vinyl benzoic acid, crotonic acid, penetenoic acid, angelic acid, tiglic acid is single Body；Itaconic acid, mesaconic acid, citraconic acid, fumaric acid, maleic acid, 2- glutaconate, methene succinic acid, allyl malonic acid, Asia The intramoleculars such as isopropyl succinic acid, 2,4- muconic acid, acetylenedicarboxylic acid have two or more the acid monomers of carboxyl etc..It can With the copolymerized polymer for using will select from these two kinds or more of monomer to be polymerized.

Further preferably using the copolymerization by acrylic acid and itaconic acid for example as described in Japanese Unexamined Patent Publication 2013-065493 bulletin It is that object is constituted, contain carboxyl in molecule and be condensed each other and the polymer of anhydride group that is formed is as binder.Think by having In charging electrolyte decomposition is occurring for the structure for the monomer for having the acid degree of two or more carboxyls high in a molecule It is easy to capture lithium ion etc. before reaction.Further, since carboxyl is more compared with polyacrylic acid, polymethylacrylic acid, acidity degree is high, and Stipulated that the carboxyl of amount is changing into anhydride group, so acidity degree will not be excessively high.Therefore, have using cathode bonding dosage form At cathode secondary cell, starting efficiency improve, input-output characteristic improve.

In addition in the range of not damaging performance, the fluorine-containing tree such as Kynoar, polytetrafluoroethylene (PTFE), fluorubber can be mixed Rouge, the thermoplastic resins such as polypropylene, polyethylene, the imide series resin such as polyimides, polyamidoimide contain alkoxy first The polymer such as the resin of silylation.

The mixing ratio of binder in negative electrode active material layer by quality ratio, preferably negative electrode active material: bonding Agent=1:0.005~1:0.3.This is because the mouldability of electrode reduces if binder is excessively few, in addition, if binder mistake More, the energy density of electrode is lower.

The binder of non-aqueous electrolyte secondary battery (1) can be above-mentioned binder, or other binders. For example, the fluorine resins such as Kynoar, polytetrafluoroethylene (PTFE), fluorubber, polypropylene, polyethylene etc. can be illustrated as binder Thermoplastic resin, the imide series resin such as polyimides, polyamidoimide, the resin containing alkoxysilyl.

In any case, the mixing ratio of the binder in negative electrode active material layer is by quality ratio, it is preferably to be cathode Active material: binder=1:0.005~1:0.3.This is because the mouldability of electrode reduces if binder is excessively few, separately Outside, if binder excessively if the energy density of electrode be lower.

Conductive auxiliary agent is added to improve the electric conductivity of electrode.Therefore, conductive auxiliary agent electrode electric conductivity not It can arbitrarily add in the case where foot, can not be added in the case where the electric conductivity of electrode is excellent enough.As conductive auxiliary agent, As long as being the electronics high conduction body of chemical stabilization, carbon black, graphite, acetylene black, the Ketjen black of carbonaceous particle can be illustrated as (registered trademark), gas-phase growth of carbon fibre (Vapor Grown Carbon Fiber:VGCF) and various metallics etc..These Conductive auxiliary agent can be added to active material layer with two kinds or more alone or in combination.Conductive auxiliary agent in negative electrode active material layer is matched Composition and division in a proportion example by quality ratio, preferably negative electrode active material: conductive auxiliary agent=1:0.01~1:0.5.This is because if conductive Auxiliary agent is excessively few can not then to form efficient conductive channel, in addition, if conductive auxiliary agent excessively if negative electrode active material layer at The type difference and energy density of electrode is lower.

It, can be by the way that negative electrode active will be added when making the cathode of non-aqueous electrolyte secondary battery using above-mentioned binder The conductive auxiliary agents such as material powder, carbon dust, above-mentioned binder and suitable solvent and the substance roller coating for mixing and being made slurry The methods of method, dip coating, scraper method, spray coating method, curtain coating are coated on the current collector, keep above-mentioned binder dry or solidification and Production.As solvent, n-methyl-2-pyrrolidone, methanol, methyl iso-butyl ketone (MIBK), water can be illustrated.In order to improve electrode density, Substance after drying can be compressed.

(anode)

Anode used in non-aqueous electrolyte secondary battery has the anode that can occlude and release lithium ion electrical charge carrier Active material.Anode has collector and is bonded in the positive electrode active material layer on the surface of collector.Positive electrode active material layer packet Include positive active material and binder and/or conductive auxiliary agent as needed.As long as the collector of anode is tolerable is suitble to The metal of the voltage of used active material is just not particularly limited, for example, can illustrate selected from silver, copper, gold, aluminium, tungsten, cobalt, At least one of zinc, nickel, iron, platinum, tin, indium, titanium, ruthenium, tantalum, chromium, molybdenum and stainless steel and other metal materials.

When the current potential of anode is calculated as 4V or more with lithium benchmark, it is preferred to use aluminium is as collector.

Specifically, as anode collector, it is preferable to use the collector being made of aluminum or aluminum alloy.Here aluminium refers to The aluminium of 99.0% or more purity is known as fine aluminium by fine aluminium.The substance for adding various elements into fine aluminium and becoming alloy is known as Aluminium alloy.As aluminium alloy, can enumerate Al-Cu system, Al-Mn system, Al-Fe system, Al-Si system, Al-Mg system, AL-Mg-Si system, Al-Zn-Mg system.

In addition, as aluminum or aluminum alloy, specifically, the A1000 system alloy such as can enumerate JIS A1085, A1N30 (fine aluminium system), the A3000 such as JIS A3003, A3004 system alloy (Al-Mn system), the A8000 such as JIS A8079, A8021 system alloy (Al-Fe system).Collector can be coating with well known protective layer.It can be used and handle the well known method in the surface of collector Collector as collector.

Collector can be using the forms such as paillon, thin slice, film, threadiness, rodlike, net.Therefore, as collector, for example, can It is preferable to use the metal foils such as copper foil, nickel foil, aluminium foil, stainless steel foil.When collector is the form of paillon, thin slice, film, thickness is excellent It is selected as in the range of 1 μm~100 μm.The collector of this and above-mentioned cathode is same.

The binder and conductive auxiliary agent illustrated in the binder and conductive auxiliary agent and cathode of anode is same.

As a positive electrode active material, the Li of lamellar compound can be enumerated_aNi_bCo_cMn_dD_eO_f(0.2≤a≤1.2, b+c+d+e =1,0≤e < 1, D be selected from Li, Fe, Cr, Cu, Zn, Ca, Mg, S, Si, Na, K, Al, Zr, Ti, P, Ga, Ge, V, Mo, Nb, W, At least one kind of element in La, 1.7≤f≤2.1), Li₂MnO₃.In addition, as a positive electrode active material, LiMn can be enumerated₂O₄Equal points Spar, and the solid solution being made of the mixture of spinelle and lamellar compound, by LiMPO₄、LiMVO₄Or Li₂MSiO₄(formula In M be selected from least one of Co, Ni, Mn, Fe) etc. expressions polyanion based compound.In addition, as positive electrode active material Matter can enumerate LiFePO₄F etc. is by LiMPO₄Hydroxyl ferrophosphorus lithium (Tavorite) based compound of F (M is transition metal) expression, LiFeBO₃Deng by LiMBO₃The borate-based compound that (M is transition metal) indicates.What is used as a positive electrode active material is any The metallic element that basic composition is contained can also can be used using above-mentioned composition formula as basic composition in metal oxide Substance made of being replaced with other metallic elements.In addition, as a positive electrode active material, can be used without charge carrier (example Such as facilitate the lithium ion of charge and discharge) positive active material.For example, it is also possible to use sulphur simple substance (S), sulphur and carbon Composite Compound, TiS₂Equal metal sulfides, V₂O₅、MnO₂Contain these virtues in equal oxides, polyaniline and anthraquinone and chemical structure Compound, conjugation the oxalic acid system organic matter equiconjugate based material, other well known material of fragrant race.Furthermore, it is possible to using having Nitroxide (nitroxide), NO free radical (nitronyl nitroxide), ten thousand oxygen radical of jar (unit of capacitance) (galvinoxyl), The compound of the stable free radical such as phenoxy group is as a positive electrode active material.

Using be free of lithium electrical charge carrier cathode active material when, need using well known method to anode and/ Or cathode adds charge carrier in advance.Charge carrier can be added with the state of ion, can be with the non-ionic state such as metal Addition.For example, lithium foil can be attached to anode and/or cathode etc. by its integration when charge carrier is lithium.Positive electrode and negative electrode Conductive auxiliary agent and binder etc. can similarly be contained.Conductive auxiliary agent and binder are not particularly limited, same with above-mentioned cathode Sample, as long as the conductive auxiliary agent and binder in non-aqueous electrolyte secondary battery can be used in.

When the surface of collector forms active material layer, rolling method, die coating method, dip coating, scraper method, spray can be used The well known method all the time such as coating, curtain coating, is coated with active material on the surface of collector.Specifically, preparation contains The active material layer of active material and binder as needed and conductive auxiliary agent formation composition (so-called negative electrode material together, Anode closes material), after paste is made to the composition addition solvent appropriate, after being coated on the surface of collector, it is dried.Make For solvent, n-methyl-2-pyrrolidone, methanol, methyl iso-butyl ketone (MIBK), water can be illustrated.In order to improve electrode density, can will do Article after dry is compressed.

Non-aqueous electrolyte secondary battery uses separator as needed.Positive electrode and negative electrode are isolated in separator, prevent because of the two poles of the earth Contact caused by electric current short circuit, and pass through lithium ion.As separator, it can enumerate and use polytetrafluoroethylene (PTFE), gathered Propylene, polyethylene, polyimides, polyamide, aromatic polyamides (Aromatic polyamide), polyester, polyacrylonitrile etc. close At the natural polymers such as the polysaccharides such as resin, cellulose, amylose, fibroin, keratin, wooden, suberin, ceramics etc. Porous body, non-woven fabrics, fabric of one or more in electrical insulating property material etc..In addition, separator can be multilayered structure.Due to The viscosity of electrolyte of the invention is slightly higher, and polarity is high, and the film immersed is easy it is advantageous to water isopolarity solvent.Specifically, into The preferred water isopolarity solvent of one step immerses 90% or more the film in existing gap.

The sandwiched separator as needed between positive electrode and negative electrode and electrode body is made.Electrode body can be anode, isolation Laminated type or anode, separator and the cathode that part and cathode are overlapped into be rolled into it is winding-type in any kind.By anode After being connected between positive terminal and negative terminal outside the collector of collector and cathode to connection using current collection conducting wire etc., Electrolyte of the invention, which is added, to electrode body can be made non-aqueous electrolyte secondary battery.In addition, nonaqueous electrolyte of the invention As long as secondary cell executes charge and discharge in the voltage range for being suitble to the type of active material contained by electrode.

The shape of non-aqueous electrolyte secondary battery of the invention is not particularly limited, and can use cylindrical type, square, button The various shapes such as type, laminated-type.

Non-aqueous electrolyte secondary battery of the invention is unrelated with the type of charge carrier as described above.Therefore, of the invention Non-aqueous electrolyte secondary battery can be for example lithium ion secondary battery, can be lithium secondary battery.Alternatively, can be used lithium with Outer charge carrier (such as sodium).Non-aqueous electrolyte secondary battery of the invention can be equipped on vehicle.Vehicle is its power source Whole or a part of electric energy generated using non-aqueous electrolyte secondary battery vehicle, for example, electric car, mixing Power vehicle etc..It, can be by multiple non-aqueous electrolyte secondary batteries to connect in vehicle loading non-aqueous electrolyte secondary battery Mode connect and form battery pack.Equipment as non-aqueous electrolyte secondary battery is carried can also be enumerated a than vehicles Battery-driven various household appliances, office equipment, the industrial equipment etc. such as people's computer, portable communication device.In addition, this The non-aqueous electrolyte secondary battery of invention can be used for wind-power electricity generation, solar power generation, hydroelectric generation and other electric system The mechanical power supply source of the power and/or auxiliary of electrical storage device and electric power smoothing device, ship etc., aircraft, spacecraft Deng power and/or the mechanical power supply source of auxiliary, power source without using the vehicle of electricity auxiliary power supply, mobile Power supply, system reserve power supply, the power supply of uninterrupted power supply, charging station for electric vehicle of household machine people etc. temporarily store up The electrical storage device of electric power needed for depositing charging.

It this concludes the description of the embodiment of electrolyte of the invention, but the present invention is not limited to the above embodiments.It is not taking off In the range of purport of the invention, can by implement change, improvement that those skilled in the art can carry out etc. it is various in a manner of To implement.

Hereinafter, showing embodiment and comparative example, the present invention is specifically described.It should be noted that the present invention is not limited to this A little embodiments.Hereinafter, unless otherwise specified, then " part " indicates mass parts, " % " indicates quality %.

(electrolyte)

(E1)

Electrolyte of the invention is manufactured as follows.

1,2- dimethoxy-ethane about 5mL as organic solvent is put into the flask for having stirrer and thermometer. Under agitation, by solution temperature be maintained at 40 DEG C it is below in a manner of 1,2- dimethoxy-ethane into above-mentioned flask it is slow Add (the CF as lithium salts in ground₃SO₂)₂NLi makes it dissolve.Due in (the CF that about 13g is added₃SO₂)₂At the time of NLi (CF₃SO₂)₂Solution temperature in flask is heated up to 50 so above-mentioned flask is put into thermostat by the dissolution lull of NLi DEG C, make (CF₃SO₂)₂NLi dissolution.Due in (the CF that about 15g is added₃SO₂)₂(CF at the time of NLi₃SO₂)₂The dissolution of NLi is again It stagnates, so 1 drop 1,2- dimethoxy-ethane, later (CF is added dropwise with dropper₃SO₂)₂NLi dissolution.Further slowly add (CF₃SO₂)₂(CF as defined in whole is added in NLi₃SO₂)₂NLi.Obtained electrolyte is moved into 20mL volumetric flask, 1,2- bis- is added Ethyl Methyl Ether is until volume becomes 20mL.As electrolyte E1.The volume of obtained electrolyte is 20mL, the electrolyte Contained (CF₃SO₂)₂NLi is 18.38g.(CF in electrolyte E1₃SO₂)₂The concentration of NLi is 3.2mol/L.In electrolyte E1, Relative to 1 molecule (CF₃SO₂)₂NLi contains 1.6 molecule of 1,2- dimethoxy-ethane.

It should be noted that above-mentioned manufacture is carried out in the glove box under non-reactive gas ambient.

(E2)

Use (the CF of 16.08g₃SO₂)₂NLi manufactures (CF with method same as E1₃SO₂)₂The concentration of NLi is The electrolyte E2 of 2.8mol/L.In electrolyte E2, relative to 1 molecule (CF₃SO₂)₂NLi contains 1,2- dimethoxy-ethane 2.1 and divides Son.

(E3)

It will be put into the flask for having stirrer as the acetonitrile of organic solvent about 5mL.Under agitation, to above-mentioned burning Acetonitrile in bottle slowly adds the (CF as lithium salts₃SO₂)₂NLi makes it dissolve.(the CF that total amount is 19.52g is added₃SO₂)₂After NLi, one evening of stirring.Obtained electrolyte is moved into 20mL volumetric flask, acetonitrile is added until volume becomes 20mL.Made For electrolyte E3.It should be noted that above-mentioned manufacture is carried out in the glove box under non-reactive gas ambient.

(CF in electrolyte E3₃SO₂)₂The concentration of NLi is 3.4mol/L.In electrolyte E3, relative to 1 molecule (CF₃SO₂)₂NLi contains 3 molecule of acetonitrile.

(E4)

Use (the CF of 24.11g₃SO₂)₂NLi manufactures (CF with method same as E3₃SO₂)₂The concentration of NLi is The electrolyte E4 of 4.2mol/L.In electrolyte E4, relative to 1 molecule (CF₃SO₂)₂NLi contains 1.9 molecule of acetonitrile.

(E5)

Use (the FSO of 13.47g₂)₂NLi is as lithium salts, using 1,2- dimethoxy-ethane as organic solvent, except this it Outside, with method same as E3, (FSO is manufactured₂)₂The concentration of NLi is the electrolyte E5 of 3.6mol/L.In electrolyte E5, relative to 1 molecule (FSO₂)₂NLi contains 1.9 molecule of 1,2- dimethoxy-ethane.

(E6)

Use (the FSO of 14.97g₂)₂NLi manufactures (FSO with method same as E5₂)₂The concentration of NLi is 4.0mol/L Electrolyte E6.In electrolyte E6, relative to 1 molecule (FSO₂)₂NLi contains 1.5 molecule of 1,2- dimethoxy-ethane.

(E7)

Use (the FSO of 15.72g₂)₂NLi is as lithium salts, in addition to this, with method same as E3, manufactures (FSO₂)₂The concentration of NLi is the electrolyte E7 of 4.2mol/L.In electrolyte E7, relative to 1 molecule (FSO₂)₂NLi contains 3 molecule of acetonitrile.

(E8)

Use (the FSO of 16.83g₂)₂NLi manufactures (FSO with method same as E7₂)₂The concentration of NLi is 4.5mol/L Electrolyte E8.In electrolyte E8, relative to 1 molecule (FSO₂)₂NLi contains 2.4 molecule of acetonitrile.

(E9)

Use (the FSO of 18.71g₂)₂NLi manufactures (FSO with method same as E7₂)₂The concentration of NLi is 5.0mol/L Electrolyte E9.In electrolyte E9, relative to 1 molecule (FSO₂)₂NLi contains 2.1 molecule of acetonitrile.

(E10)

Use (the FSO of 20.21g₂)₂NLi manufactures (FSO with method same as E7₂)₂The concentration of NLi is 5.4mol/L Electrolyte E10.In electrolyte E10, relative to 1 molecule (FSO₂)₂NLi contains 2 molecule of acetonitrile.

(E11)

It will be added in the flask for having stirrer as the dimethyl carbonate of organic solvent about 5mL.Under agitation, to Dimethyl carbonate in above-mentioned flask slowly adds the (FSO as lithium salts₂)₂NLi makes it dissolve.Addition total amount is 14.64g (FSO₂)₂After NLi, one evening of stirring.Obtained electrolyte is moved into 20mL volumetric flask, dimethyl carbonate is added until volume becomes At 20mL.As electrolyte E11.It should be noted that above-mentioned manufacture is carried out in the glove box under non-reactive gas ambient 's.

(FSO in electrolyte E11₂)₂The concentration of NLi is 3.9mol/L.In electrolyte E11, relative to 1 molecule (FSO₂)₂NLi contains 2 molecule of dimethyl carbonate.

(E12)

Dimethyl carbonate is added to electrolyte E11 to be diluted, (FSO is made₂)₂The concentration of NLi is the electrolysis of 3.4mol/L Liquid E12.In electrolyte E12, relative to 1 molecule (FSO₂)₂NLi contains 2.5 molecule of dimethyl carbonate.

(E13)

Dimethyl carbonate is added to electrolyte E11 to be diluted, (FSO is made₂)₂The concentration of NLi is the electrolysis of 2.9mol/L Liquid E13.In electrolyte E13, relative to 1 molecule (FSO₂)₂NLi contains 3 molecule of dimethyl carbonate.

(E14)

Dimethyl carbonate is added to electrolyte E11 to be diluted, (FSO is made₂)₂The concentration of NLi is the electrolysis of 2.6mol/L Liquid E14.In electrolyte E14, relative to 1 molecule (FSO₂)₂NLi contains 3.5 molecule of dimethyl carbonate.

(E15)

Dimethyl carbonate is added to electrolyte E11 to be diluted, (FSO is made₂)₂The concentration of NLi is the electrolysis of 2.0mol/L Liquid E15.In electrolyte E15, relative to 1 molecule (FSO₂)₂NLi contains 5 molecule of dimethyl carbonate.

(E16)

It will be added in the flask for having stirrer as the methyl ethyl carbonate of organic solvent about 5mL.Under agitation, to Methyl ethyl carbonate in above-mentioned flask slowly adds the (FSO as lithium salts₂)₂NLi makes it dissolve.Addition total amount is 12.81g (FSO₂)₂After NLi, one evening of stirring.Obtained electrolyte is moved into 20mL volumetric flask, methyl ethyl carbonate is added until volume becomes At 20mL.As electrolyte E16.It should be noted that above-mentioned manufacture is carried out in the glove box under non-reactive gas ambient 's.

(FSO in electrolyte E16₂)₂The concentration of NLi is 3.4mol/L.In electrolyte E16, relative to 1 molecule (FSO₂)₂NLi contains 2 molecule of methyl ethyl carbonate.

(E17)

Methyl ethyl carbonate is added to electrolyte E16 to be diluted, (FSO is made₂)₂The concentration of NLi is the electrolysis of 2.9mol/L Liquid E17.In electrolyte E17, relative to 1 molecule (FSO₂)₂NLi contains 2.5 molecule of methyl ethyl carbonate.

(E18)

Methyl ethyl carbonate is added to electrolyte E16 to be diluted, (FSO is made₂)₂The concentration of NLi is the electrolysis of 2.2mol/L Liquid E18.In electrolyte E18, relative to 1 molecule (FSO₂)₂NLi contains 3.5 molecule of methyl ethyl carbonate.

(E19)

It will be added in the flask for having stirrer as the diethyl carbonate of organic solvent about 5mL.Under agitation, to Diethyl carbonate in above-mentioned flask slowly adds the (FSO as lithium salts₂)₂NLi makes it dissolve.Addition total amount is 11.37g (FSO₂)₂After NLi, one evening of stirring.Obtained electrolyte is moved into 20mL volumetric flask, diethyl carbonate is added until volume becomes At 20mL.As electrolyte E19.It should be noted that above-mentioned manufacture is carried out in the glove box under non-reactive gas ambient 's.

(FSO in electrolyte E19₂)₂The concentration of NLi is 3.0mol/L.In electrolyte E19, relative to 1 molecule (FSO₂)₂NLi contains 2 molecule of diethyl carbonate.

(E20)

Diethyl carbonate is added to electrolyte E19 to be diluted, (FSO is made₂)₂The concentration of NLi is the electrolysis of 2.6mol/L Liquid E20.In electrolyte E20, relative to 1 molecule (FSO₂)₂NLi contains 2.5 molecule of diethyl carbonate.

(E21)

Diethyl carbonate is added to electrolyte E19 to be diluted, (FSO is made₂)₂The concentration of NLi is the electrolysis of 2.0mol/L Liquid E21.In electrolyte E21, relative to 1 molecule (FSO₂)₂NLi contains 3.5 molecule of diethyl carbonate.

(C1)

Use (the CF of 5.74g₃SO₂)₂NLi, using 1,2- dimethoxy-ethane as organic solvent, in addition to this, with The same method of E3 manufactures (CF₃SO₂)₂The concentration of NLi is the electrolyte C1 of 1.0mol/L.In electrolyte C1, relative to 1 molecule (CF₃SO₂)₂NLi contains 8.3 molecule of 1,2- dimethoxy-ethane.

(C2)

Use (the CF of 5.74g₃SO₂)₂NLi manufactures (CF with method same as E3₃SO₂)₂The concentration of NLi is The electrolyte C2 of 1.0mol/L.In electrolyte C2, relative to 1 molecule (CF₃SO₂)₂NLi contains 16 molecule of acetonitrile.

(C3)

Use (the FSO of 3.74g₂)₂NLi manufactures (FSO with method same as E5₂)₂The concentration of NLi is 1.0mol/L Electrolyte C3.In electrolyte C3, relative to 1 molecule (FSO₂)₂NLi contains 8.8 molecule of 1,2- dimethoxy-ethane.

(C4)

Use (the FSO of 3.74g₂)₂NLi manufactures (FSO with method same as E7₂)₂The concentration of NLi is 1.0mol/L Electrolyte C4.In electrolyte C4, relative to 1 molecule (FSO₂)₂NLi contains 17 molecule of acetonitrile.

(C5)

Use the mixed solvent (volume ratio 3:7, hereinafter sometimes referred to " EC/DEC ") of ethylene carbonate and diethyl carbonate As organic solvent, the LiPF of 3.04g is used₆As lithium salts, in addition to this, with method same as E3, LiPF is manufactured₆It is dense Degree is the electrolyte C5 of 1.0mol/L.

(C6)

Dimethyl carbonate is added to electrolyte E11 to be diluted, (FSO is made₂)₂The concentration of NLi is the electrolysis of 1.1mol/L Liquid C6.In electrolyte C6, relative to 1 molecule (FSO₂)₂NLi contains 10 molecule of dimethyl carbonate.

(C7)

Methyl ethyl carbonate is added to electrolyte E16 to be diluted, (FSO is made₂)₂The concentration of NLi is the electrolysis of 1.1mol/L Liquid C7.In electrolyte C7, relative to 1 molecule (FSO₂)₂NLi contains 8 molecule of methyl ethyl carbonate.

(C8)

Diethyl carbonate is added to electrolyte E19 to be diluted, (FSO is made₂)₂The concentration of NLi is the electrolysis of 1.1mol/L Liquid C8.In electrolyte C8, relative to 1 molecule (FSO₂)₂NLi contains 7 molecule of diethyl carbonate.

The list of electrolyte is shown in table 3.

Table 3

LiTFSA:(CF₃SO₂)₂NLi, LiFSA:(FSO₂)₂NLi, AN: acetonitrile, DME:1,2- dimethoxy-ethane, EC/ DTC: the mixed solvent (volume ratio 3: 7) of ethylene carbonate and diethyl carbonate

(evaluation example 1:IR measurement)

To electrolyte E3, E4, E7, E8, E10, C2, C4 and acetonitrile, (CF₃SO₂)₂NLi、(FSO₂)₂NLi, by below Condition carries out IR measurement.By 2100~2400cm^-1The IR spectrum of range be shown in Fig. 1~Figure 10.The horizontal axis of figure is wave number (cm^-1), the longitudinal axis is absorbance (reflection absorbance).Further to electrolyte E11~E21, electrolyte C6~C8 and carbonic acid two Methyl esters, methyl ethyl carbonate, diethyl carbonate carry out IR measurement by condition below.By 1900~1600cm^-1Range IR light Spectrum is shown in Figure 11~Figure 27.In addition, being directed to (FSO₂)₂NLi, by 1900~1600cm^-1The IR spectrum of range be shown in figure 28.The horizontal axis of figure is wave number (cm^-1), the longitudinal axis is absorbance (reflection absorbance).

IR determination condition

Device: FT-IR (Bruker Optics corporation)

Determination condition: ATR method (uses diamond)

Determination of the environment: under non-reactive gas ambient

Fig. 8 shows acetonitrile IR spectrum 2250cm^-1Near, observe stretching for three keys between C and N from acetonitrile Contract the characteristic peak vibrated.It should be noted that (the CF indicated in Fig. 9₃SO₂)₂(the FSO that the IR spectrum and Figure 10 of NLi indicates₂)₂NLi's The 2250cm of IR spectrum^-1Near, special peak is not observed.

Fig. 1 shows electrolyte E3 IR spectrum in, in 2250cm^-1Nearby observe faint (Io=0.00699) The characteristic peak of the stretching vibration of three keys between C and N from acetonitrile.Furthermore in the IR spectrum of Fig. 1, from 2250cm^-1Near The 2280cm being displaced to high wave number side^-1Three keys between C and N from acetonitrile are nearby observed with peak intensity Is=0.05828 The characteristic peak of stretching vibration.The relationship of the peak intensity of Is and Io is Is > Io, Is=8 × Io.

In the IR spectrum for the electrolyte E4 that Fig. 2 is indicated, in 2250cm^-1The peak from acetonitrile nearby is not observed, From 2250cm^-1The 2280cm being nearby displaced to high wave number side^-1The C from acetonitrile is nearby observed with peak intensity Is=0.05234 The characteristic peak of the stretching vibration of three keys between N.The relationship of the peak intensity of Is and Io is Is > Io.

In the IR spectrum for the electrolyte E7 that Fig. 3 is indicated, in 2250cm^-1Nearby observe faint (Io=0.00997) The characteristic peak of the stretching vibration of three keys between C and N from acetonitrile.Furthermore in the IR spectrum of Fig. 3, from 2250cm^-1Near The 2280cm being displaced to high wave number side^-1Three keys between C and N from acetonitrile are nearby observed with peak intensity Is=0.08288 The characteristic peak of stretching vibration.The relationship of the peak intensity of Is and Io is Is > Io, Is=8 × Io.The electrolyte E8 indicated for Fig. 4 IR spectrum, the peak of intensity same as the IR chart of Fig. 3 is also observed in same wave number.The relationship of the peak intensity of Is and Io It is Is > Io, Is=11 × Io.

In the IR spectrum for the electrolyte E10 that Fig. 5 is indicated, in 2250cm^-1The peak from acetonitrile nearby is not observed, From 2250cm^-1The 2280cm being nearby displaced to high wave number side^-1The C from acetonitrile is nearby observed with peak intensity Is=0.07350 The characteristic peak of the stretching vibration of three keys between N.The relationship of the peak intensity of Is and Io is Is > Io.

In the IR spectrum for the electrolyte C2 that Fig. 6 is indicated, in the same manner as Fig. 8, in 2250cm^-1Nearby with peak intensity Io= 0.04441 observes the characteristic peak of the stretching vibration of three keys between C and N from acetonitrile.Furthermore in the IR spectrum of Fig. 6, From 2250cm^-1The 2280cm being nearby displaced to high wave number side^-1The C from acetonitrile is nearby observed with peak intensity Is=0.03018 The characteristic peak of the stretching vibration of three keys between N.The relationship of the peak intensity of Is and Io is Is < Io.

In the IR spectrum for the electrolyte C4 that Fig. 7 is indicated, in the same manner as Fig. 8, in 2250cm^-1Nearby with peak intensity Io= 0.04975 observes the characteristic peak of the stretching vibration of three keys between C and N from acetonitrile.Furthermore in the IR spectrum of Fig. 7, From 2250cm^-1The 2280cm being nearby displaced to high wave number side^-1The C from acetonitrile is nearby observed with peak intensity Is=0.03804 The characteristic peak of the stretching vibration of three keys between N.The relationship of the peak intensity of Is and Io is Is < Io.

In the 1750cm of the IR spectrum for the dimethyl carbonate that Figure 17 is indicated^-1Near, observe C from dimethyl carbonate and The characteristic peak of the stretching vibration of double bond between O.It should be noted that (the FSO indicated in Figure 28₂)₂The 1750cm of the IR spectrum of NLi^-1 Near, special peak is not observed.

In the IR spectrum for the electrolyte E11 that Figure 11 is indicated, in 1750cm^-1Nearby observe faint (Io=0.16628) The C and O from dimethyl carbonate between double bond stretching vibration characteristic peak.Furthermore in the IR spectrum of Figure 11, from 1750cm^-1The 1717cm being nearby displaced to lower wave number side^-1Nearby observed with peak intensity Is=0.48032 from carbonic acid diformazan The characteristic peak of the stretching vibration of double bond between the C and O of ester.The relationship of the peak intensity of Is and Io is Is > Io, Is=2.89 × Io.

In the IR spectrum for the electrolyte E12 that Figure 12 is indicated, in 1750cm^-1Nearby observe faint (Io=0.18129) The C and O from dimethyl carbonate between double bond stretching vibration characteristic peak.Furthermore in the IR spectrum of Figure 12, from 1750cm^-1The 1717cm being nearby displaced to lower wave number side^-1Nearby observed with peak intensity Is=0.52005 from carbonic acid diformazan The characteristic peak of the stretching vibration of double bond between the C and O of ester.The relationship of the peak intensity of Is and Io is Is > Io, Is=2.87 × Io.

In the IR spectrum for the electrolyte E13 that Figure 13 is indicated, in 1750cm^-1Nearby observe faint (Io=0.20293) The C and O from dimethyl carbonate between double bond stretching vibration characteristic peak.Furthermore in the IR spectrum of Figure 13, from 1750cm^-1The 1717cm being nearby displaced to lower wave number side^-1Nearby observed with peak intensity Is=0.53091 from carbonic acid diformazan The characteristic peak of the stretching vibration of double bond between the C and O of ester.The relationship of the peak intensity of Is and Io is Is > Io, Is=2.62 × Io.

In the IR spectrum for the electrolyte E14 that Figure 14 is indicated, in 1750cm^-1Nearby observe faint (Io=0.23891) The C and O from dimethyl carbonate between double bond stretching vibration characteristic peak.Furthermore in the IR spectrum of Figure 14, from 1750cm^-1The 1717cm being nearby displaced to lower wave number side^-1Nearby observed with peak intensity Is=0.53098 from carbonic acid diformazan The characteristic peak of the stretching vibration of double bond between the C and O of ester.The relationship of the peak intensity of Is and Io is Is > Io, Is=2.22 × Io.

In the IR spectrum for the electrolyte E15 that Figure 15 is indicated, in 1750cm^-1Nearby observe faint (Io=0.30514) The C and O from dimethyl carbonate between double bond stretching vibration characteristic peak.Furthermore in the IR spectrum of Figure 15, from 1750cm^-1The 1717cm being nearby displaced to lower wave number side^-1Nearby observed with peak intensity Is=0.50223 from carbonic acid diformazan The characteristic peak of the stretching vibration of double bond between the C and O of ester.The relationship of the peak intensity of Is and Io is Is > Io, Is=1.65 × Io.

In the IR spectrum for the electrolyte C6 that Figure 16 is indicated, in 1750cm^-1Nearby observe C from dimethyl carbonate and The characteristic peak (Io=0.48204) of the stretching vibration of double bond between O.Furthermore in the IR spectrum of Figure 16, from 1750cm^-1Near The 1717cm being displaced to lower wave number side^-1Nearby observed between C and O from dimethyl carbonate with peak intensity Is=0.39244 The characteristic peak of the stretching vibration of double bond.The relationship of the peak intensity of Is and Io is Is < Io.

In the 1745cm of the IR spectrum for the methyl ethyl carbonate that Figure 22 is indicated^-1Near, observe C from methyl ethyl carbonate and The characteristic peak of the stretching vibration of double bond between O.

In the IR spectrum for the electrolyte E16 that Figure 18 is indicated, in 1745cm^-1Nearby observe faint (Io=0.13582) The C and O from methyl ethyl carbonate between double bond stretching vibration characteristic peak.Furthermore in the IR spectrum of Figure 18, from 1745cm^-1The 1711cm being nearby displaced to lower wave number side^-1Nearby observed with peak intensity Is=0.45888 from methyl ethyl carbonate The characteristic peak of the stretching vibration of double bond between the C and O of ester.The relationship of the peak intensity of Is and Io is Is > Io, Is=3.38 × Io.

In the IR spectrum for the electrolyte E17 that Figure 19 is indicated, in 1745cm^-1Nearby observe faint (Io=0.15151) The C and O from methyl ethyl carbonate between double bond stretching vibration characteristic peak.Furthermore in the IR spectrum of Figure 19, from 1745cm^-1The 1711cm being nearby displaced to lower wave number side^-1Nearby observed with peak intensity Is=0.48779 from methyl ethyl carbonate The characteristic peak of the stretching vibration of double bond between the C and O of ester.The relationship of the peak intensity of Is and Io is Is > Io, Is=3.22 × Io.

In the IR spectrum for the electrolyte E18 that Figure 20 is indicated, in 1745cm^-1Nearby observe faint (Io=0.20191) The C and O from methyl ethyl carbonate between double bond stretching vibration characteristic peak.Furthermore in the IR spectrum of Figure 20, from 1745cm^-1The 1711cm being nearby displaced to lower wave number side^-1Nearby observed with peak intensity Is=0.48407 from methyl ethyl carbonate The characteristic peak of the stretching vibration of double bond between the C and O of ester.The relationship of the peak intensity of Is and Io is Is > Io, Is=2.40 × Io.

In the IR spectrum for the electrolyte C7 that Figure 21 is indicated, in 1745cm^-1Nearby observe C from methyl ethyl carbonate and The characteristic peak (Io=0.41907) of the stretching vibration of double bond between O.Furthermore in the IR spectrum of Figure 21, from 1745cm^-1Near The 1711cm being displaced to lower wave number side^-1Nearby observed between C and O from methyl ethyl carbonate with peak intensity Is=0.33929 The characteristic peak of the stretching vibration of double bond.The relationship of the peak intensity of Is and Io is Is < Io.

In the 1742cm of the IR spectrum for the diethyl carbonate that Figure 27 is indicated^-1Near, observe C from diethyl carbonate and The characteristic peak of the stretching vibration of double bond between O.

In the IR spectrum for the electrolyte E19 that Figure 23 is indicated, in 1742cm^-1Nearby observe faint (Io=0.11202) The C and O from diethyl carbonate between double bond stretching vibration characteristic peak.Furthermore in the IR spectrum of Figure 23, from 1742cm^-1The 1706cm being nearby displaced to lower wave number side^-1Nearby observed with peak intensity Is=0.42925 from carbonic acid diethyl The characteristic peak of the stretching vibration of double bond between the C and O of ester.The relationship of the peak intensity of Is and Io is Is > Io, Is=3.83 × Io.

In the IR spectrum for the electrolyte E20 that Figure 24 is indicated, in 1742cm^-1Nearby observe faint (Io=0.15231) The C and O from diethyl carbonate between double bond stretching vibration characteristic peak.Furthermore in the IR spectrum of Figure 24, from 1742cm^-1The 1706cm being nearby displaced to lower wave number side^-1Nearby observed with peak intensity Is=0.45679 from carbonic acid diethyl The characteristic peak of the stretching vibration of double bond between the C and O of ester.The relationship of the peak intensity of Is and Io is Is > Io, Is=3.00 × Io.

In the IR spectrum for the electrolyte E21 that Figure 25 is indicated, in 1742cm^-1Nearby observe faint (Io=0.20337) The C and O from diethyl carbonate between double bond stretching vibration characteristic peak.Furthermore in the IR spectrum of Figure 25, from 1742cm^-1The 1706cm being nearby displaced to lower wave number side^-1Nearby observed with peak intensity Is=0.43841 from carbonic acid diethyl The characteristic peak of the stretching vibration of double bond between the C and O of ester.The relationship of the peak intensity of Is and Io is Is > Io, Is=2.16 × Io.

In the IR spectrum for the electrolyte C8 that Figure 26 is indicated, in 1742cm^-1Nearby observe C from diethyl carbonate and The characteristic peak (Io=0.39636) of the stretching vibration of double bond between O.Furthermore in the IR spectrum of Figure 26, from 1742cm^-1Near The 1709cm being displaced to lower wave number side^-1Nearby observed between C and O from diethyl carbonate with peak intensity Is=0.31129 The characteristic peak of the stretching vibration of double bond.The relationship of the peak intensity of Is and Io is Is < Io.

(evaluation example 2: Raman spectroscopy)

To electrolyte E8, E9, C4 and E11, E13, E15, C6, Raman spectroscopy is carried out by condition below.It will see The Raman spectrum for observing the peak of the anion part of the metal salt from each electrolyte is shown in Figure 29~Figure 35.The horizontal axis of figure For wave number (cm^-1), the longitudinal axis is scattering strength.

Raman spectroscopy condition

Device: laser Raman spectrometer (Japan Spectroscopy Corporation NRS series)

Optical maser wavelength: 532nm

Electrolyte is enclosed in quartz colorimetric utensil under non-reactive gas ambient, for measurement.

In 700~800cm of the Raman spectrum of electrolyte E8, E9, C4 that Figure 29~Figure 31 is indicated^-1, observe and carry out self-dissolving Solution is in (the FSO of the LiFSA of acetonitrile₂)₂The characteristic peak of N.Here, the increase of the concentration with LiFSA is known by Figure 29~Figure 31, Above-mentioned peak is displaced to high wave number side.With electrolyte high concentration, become (the FSO for the anion for belonging to salt₂)₂N and Li phase interaction State, in other words, thus it is speculated that Li and anion have primarily formed SSIP (Solvent-separated ion when concentration is low Pairs: the shared ion pair of solvent) state primarily formed CIP (Contact ion pairs: contact with high concentration Type ion pair) state, AGG (aggregate: aggregation) state.Moreover, researching and analysing out the variation of the state with Raman spectrum The form of peak shift is observed.

In 700~800cm of the Raman spectrum of electrolyte E11, E13, E15, C6 that Figure 32~Figure 35 is indicated^-1, observe (FSO from the LiFSA for being dissolved in dimethyl carbonate₂)₂The characteristic peak of N.Here, with LiFSA's known to Figure 32~Figure 35 The increase of concentration, above-mentioned peak are displaced to high wave number side.Speculate that the phenomenon is identical as the result that the preceding paragraph is analyzed, is that electrolyte is highly concentrated Degreeization and the (FSO for making the anion for belonging to salt₂)₂The state of N and multiple Li interaction is reflected to the result of spectrum.

(evaluation example 3: ionic conductivity)

Electrolyte E1, E2, E4~E6, E8, E11, E16, E19 ionic conductivity are measured by condition below.By result It is shown in table 4.

Ionic conductivity determination condition

Under Ar environment, electrolyte is enclosed and is had in glass system conductance cell known to the cell constant of conductometric vessel of platinode, with 30 DEG C, 1kHz measured impedance.Ionic conductivity is calculated by the measurement result of impedance.Sensing equipment uses Solartron 147055BEC (Solartron company).

Table 4

Electrolyte E1, E2, E4~E6, E8, E11, E16 and E19 show ionic conductivity.Accordingly, it is to be understood that this The electrolyte that the electrolyte of invention can be used as various batteries functions.

(evaluation example 4: viscosity)

It is viscous by condition below measurement electrolyte E1, E2, E4~6, E8, E11, E16, E19 and C1~C4, C6~C8 Degree.Show the result in table 5.

Viscosimetric analysis condition

Using falling ball viscometer (AntonPaar GmbH (Anton Paar company) Lovis2000M processed), in Ar environment Under, electrolyte is enclosed into test tank, measures viscosity under conditions of 30 DEG C.

Table 5

The viscosity of electrolyte E1, E2, E4~6, the viscosity of E8, E11, E16, E19 and electrolyte C1~C4, C6~C8 are compared Compared with, hence it is evident that it is high.Therefore, if it is the battery for having used electrolyte of the invention, even if battery is damaged, electrolyte can also be inhibited Leakage.

(evaluation example 5: volatility)

With the volatility of the following method measurement electrolyte E2, E4, E8, E11, E13, C1, C2, C4 and C6.

The electrolyte of about 10mg is put into the pot of aluminum, thermogravimetric measurement device (TA Instruments company is configured at System, SDT600), measure the weight change of electrolyte at room temperature.Weight change (quality %) is subjected to differential with the time and is counted Calculate evaporation rate.Maximum speed in selective volatilization speed, is shown in table 6.

Table 6

The maximum evaporation rate of electrolyte E2, E4, E8, E11, E13 and the maximum evaporation rate of electrolyte C1, C2, C4, C6 It compares, hence it is evident that small.Therefore, even if the battery of electrolyte of the invention has been used to damage, the evaporation rate of electrolyte It is small, so inhibiting quick volatilization of the organic solvent to outside battery.

(evaluation example 6: flammability)

It is tested with flammability of the following method to electrolyte E4, C2.

3 drops are added dropwise to glass filter material (glass filters) in electrolyte with dropper, electrolyte is made to be maintained at glass filter Material.The glass filter material is clamped with tweezers, then, the glass filter material is made to contact flame.

Electrolyte E4 and flame contact 15 seconds it is also not on fire.On the other hand, electrolyte C2 passes through more than 5 seconds with regard to after-flame.

It is nonflammable to demonstrate electrolyte of the invention.

Hereinafter, non-aqueous electrolyte secondary battery (1) and non-aqueous electrolyte secondary battery (2) are specifically described.Below Embodiment and EB, CB, for convenience, subitem explanation therefore repeats sometimes.In addition, embodiment below and aftermentioned EB, CB belongs to the embodiment of both non-aqueous electrolyte secondary battery (1) and non-aqueous electrolyte secondary battery (2) sometimes.

(EB1)

Following manufacture has used the half-cell of electrolyte E8.

It will be as 10 μm of average grain diameter of 90 mass parts of graphite of active material and as the Kynoar 10 of binder Mass parts mixing.So that the mixture is scattered in suitable n-methyl-2-pyrrolidone, makes slurry.Prepare 20 μm of thickness of copper Foil is as collector.Using scraper, above-mentioned slurry is coated on the surface of the copper foil membranaceous.The copper foil for being coated with slurry is dry It is dry and remove n-methyl-2-pyrrolidone, thereafter, pressurizes to copper foil, obtain binding element.Obtained binding element is dried in vacuo Machine 120 DEG C heat drying 6 hours, obtain the copper foil for being formed with active material layer.As working electrode.

It is metal Li to electrode.

By working electrode, to electrode, be clipped in 400 μm of thickness of Whatman glass fibers as separator between the two Dimension filter paper and electrolyte E8 are housed in battery case (precious Izumi Ltd. CR2032 type button cell box), obtain non-aqueous solution electrolysis Electrolitc secondary cell EB1.The non-aqueous electrolyte secondary battery is the non-aqueous electrolyte secondary battery of evaluation, also referred to as half-cell.

(CB1)

Using electrolyte C5, in addition to this, with method same as EB1, non-aqueous electrolyte secondary battery CB1 is manufactured.

(evaluation example 7: multiplying power property)

It is tested with multiplying power property of the following method to EB1, CB1.

For each non-aqueous electrolyte secondary battery, with 0.1C, 0.2C, 0.5C, 1C, 2C multiplying power, (1C refers in a constant current Kept battery fully charged within lower 1 hour or electric discharge needed for current value) charged after discharge, measure the work under each speed Make the capacity (discharge capacity) of electrode.It should be noted that description here is will to regard cathode as to electrode, working electrode is regarded as just Pole.Calculate the ratio (multiplying power property) of capacity under other multiplying powers relative to the capacity of the working electrode under 0.1C multiplying power.It will knot Fruit is shown in table 7.

Table 7

	EB1	CB1
			0.1C capacity (mAh/g)	334	330
0.2C capacity/0.1C capacity	0.983	0.966
			0.5C capacity/0.1C capacity	0.946	0.767
1C capacity/0.1C capacity	0.868	0.498
			2C capacity/0.1C capacity	0.471	0.177

Under any multiplying power of 0.2C, 0.5C, 1C, 2C, EB1 inhibits the reduction of capacity compared with CB1, display Excellent multiplying power property.It demonstrates and shows excellent multiplying power property using the secondary cell of electrolyte of the invention.

(evaluation example 8: the responsiveness relative to fast charging and discharging repeatedly)

Capacity and voltage when observing with 1C multiplying power to non-aqueous electrolyte secondary battery EB1 and CB1 repeated charge 3 times Variation.Show the result in Figure 36.

With repeated charge, polarization when having the tendency that with 1C multiplying power streaming current becomes larger CB1, obtains from 2V to 0.01V To capacity quickly reduce.On the other hand, even if EB1 is by repeated charge, the appearance that 3 curves are overlapped from Figure 36 also can Enough confirmation polarization have been well maintained capacity almost without increase and decrease.As the reasons why increasing of polarizing in CB1, it is believed that be due to fast The Li density unevenness generated in electrolyte when fast repeated charge causes electrolyte to supply without normal direction and the reaction interface of electrode The Li of sufficient amount, that is to say, that the Li density unevenness of electrolyte.Think in EB1, by using the highly concentrated electricity of the invention of Li Liquid is solved, the unevenness of the Li concentration of electrolyte is able to suppress.The secondary cell using electrolyte of the invention is demonstrated for quick Charge and discharge show excellent responsiveness.

(evaluation example 9:Li transport number)

By the Li transport number of condition below measurement electrolyte E2, E8, C4 and C5.Show the result in table 8.

(Li transport number determination condition)

NMR pipe equipped with electrolyte is supplied in PFG-NMR device (ECA-500, Japan Electronics), with⁷Li、¹⁹F is pair As using spin-echo method, while making magnetic field pulse change width, while measuring the diffusion of the Li ion and anion in each electrolyte Coefficient.Li transport number is calculated with following formula.

Li transport number=(Li ionic diffusion coefficient)/(Li ionic diffusion coefficient+anion diffusion coefficient)

Table 8

The Li transport number of electrolyte E2, E8 are obvious high compared with the Li transport number of electrolyte C4, C5.Here, electrolyte Li ionic conductivity can be calculated and making ionic conductivity contained by electrolyte (total ionic conductivity) multiplied by Li transport number. Thus it is possible to say electrolyte of the invention compared with the existing electrolyte of the ionic conductivity of display equal extent, lithium ion is (positive Ion) conveying speed it is high.

In addition, the Li transport number for electrolyte E8, when based on the variation of above-mentioned Li transport number determination condition measuring temperature.It will As a result it is shown in table 9.

Table 9

Temperature (DEG C)	Li transport number
		30	0.50
10	0.50
		-10	0.50
-30	0.52

Electrolyte of the invention keeps good Li transport number independent of temperature as shown in Table 9.It may be said that this The electrolyte of invention also maintains liquid condition at low temperature.

(non-aqueous electrolyte secondary battery)

(EB2)

Following manufacture has used the non-aqueous electrolyte secondary battery EB2 of electrolyte E8.

It will be as a positive electrode active material by LiNi_5/10Co_2/10Mn_3/10O₂The layered rock salt structure of expression contains lithium metal 94 mass parts of oxide, 3 mass parts of acetylene black as conductive auxiliary agent and 3 mass parts of Kynoar as binder are mixed It closes.So that the mixture is scattered in suitable n-methyl-2-pyrrolidone, makes slurry.Prepare 20 μm of thickness of aluminium foil (JIS No. A1000) it is used as positive electrode collector.Using scraper, by above-mentioned slurry to become the surface that membranaceous mode is coated on the aluminium foil. The aluminium foil for being coated with slurry removes n-methyl-2-pyrrolidone by volatilization in dry 20 minutes at 80 DEG C.Thereafter, to the aluminium Foil pressurizes to obtain binding element.By obtained binding element vacuum drier 120 DEG C heat drying 6 hours, obtain being formed with just The aluminium foil of pole active material layer.As anode.Hereinafter, as needed, it will be by LiNi_5/10Co_2/10Mn_3/10O₂The layer of expression Shape rock salt structure saves slightly NCM523 containing lithium metal oxide, and acetylene black is saved slightly AB, Kynoar is saved slightly PVdF。

It will be as 98 mass parts of natural graphite of negative electrode active material and as the styrene butadiene ribber 1 of binder Mass parts and the mixing of 1 mass parts of carboxymethyl cellulose.So that the mixture is scattered in suitable ion exchange water, makes slurry.It is quasi- The copper foil of standby 20 μm of thickness is as negative electrode collector.Using scraper, above-mentioned slurry is coated on the surface of the copper foil membranaceous.It will It is coated with the copper foil drying of slurry and removes water, thereafter, pressurize to copper foil, obtain binding element.The binding element vacuum that will be obtained Drying machine 100 DEG C heat drying 6 hours, obtain the copper foil for being formed with negative electrode active material layer.As cathode.Hereinafter, As needed, styrene butadiene ribber is saved into slightly SBR, carboxymethyl cellulose is saved into slightly CMC.

As separator, prepare 20 μm of thickness of cellulose non-woven fabrics.

Separator is clamped with anode and cathode, polar plate group is made.Two one group of laminated film of the polar plate group is covered, it will After three sides are sealed, electrolyte E8 is injected to the laminated film taken the shape of a bag.Thereafter, it is sealed remaining on one side, thus It is hermetically sealed to four sides, polar plate group and electrolyte are by closed non-aqueous electrolyte secondary battery.Using the battery as non-aqueous Electrolyte secondary battery EB2.

(EB3)

Following manufacture has used the non-aqueous electrolyte secondary battery EB3 of electrolyte E8.

The anode of anode and non-aqueous electrolyte secondary battery EB2 is carried out similarly manufacture.

By 90 mass parts of natural graphite as negative electrode active material and 10 mass parts of Kynoar as binder Mixing.So that the mixture is scattered in suitable ion exchange water, makes slurry.Prepare 20 μm of thickness of copper foil as cathode current collection Body.Using scraper, above-mentioned slurry is coated on the surface of the copper foil membranaceous.It is coated with the copper foil drying of slurry and removes Water pressurizes to copper foil, obtains binding element thereafter.By obtained binding element vacuum drier 120 DEG C heat drying 6 hours, Obtain the copper foil for being formed with negative electrode active material layer.As cathode.

As separator, prepare 20 μm of thickness of cellulose non-woven fabrics.

Separator is clamped with anode and cathode, polar plate group is made.Two one group of laminated film of the polar plate group is covered, it will After three sides are sealed, electrolyte E8 is injected to the laminated film taken the shape of a bag.Thereafter, it is sealed remaining on one side, thus The non-aqueous electrolyte secondary battery being sealed in four sides of laminated film by sealing, polar plate group and electrolyte in the laminated film.It will The battery is as non-aqueous electrolyte secondary battery EB3.

(CB2)

Using electrolyte C5, in addition to this, non-aqueous electrolyte secondary battery CB2 is manufactured in the same manner as EB2.

(CB3)

Using electrolyte C5, in addition to this, non-aqueous electrolyte secondary battery CB3 is manufactured in the same manner as EB3.

(evaluation example 10: the input-output characteristic of non-aqueous electrolyte secondary battery)

By the output characteristics of condition evaluating non-aqueous electrolyte secondary battery EB2, EB3, CB2, CB3 below.

(1) 0 DEG C or input characteristics evaluation when 25 DEG C, SOC80%

Evaluation condition is set as 80%, 0 DEG C or 25 DEG C of charged state (SOC), using voltage range 3V -4.2V, capacity 13.5mAh.The evaluation of input characteristics is to carry out input in 3 times 2 seconds and input in 5 seconds respectively to each battery.

In addition, the volume based on each battery, calculates the battery output density (W/L) when 25 DEG C, input in 2 seconds.

By input characteristics evaluation result is shown in table 10." inputting within 2 seconds " in table 10 refers to defeated after charging starts 2 seconds Enter, " inputting within 5 seconds " refers to the input after charging starts 5 seconds.

As shown in table 10, unrelated with the difference of temperature, the input of EB2 is compared with the input of CB2, hence it is evident that high.Equally, EB3 Input compared with the input of CB3, hence it is evident that it is high.

In addition, the battery input density of EB2 is compared with the battery input density of CB2, hence it is evident that high.Equally, the battery of EB3 is defeated Enter density compared with the battery input density of CB3, hence it is evident that high.

(2) 0 DEG C or output characteristics evaluation when 25 DEG C, SOC20%

Evaluation condition is set as 20%, 0 DEG C or 25 DEG C of charged state (SOC), using voltage range 3V -4.2V, capacity 13.5mAh.SOC20%, 0 DEG C of e.g. output characteristics as when refrigerating chamber etc. uses are not easy the region embodied.Output is special Property evaluation be each battery is carried out respectively 3 times 2 seconds output and 5 seconds export.

In addition, the volume based on each battery, calculates the battery output density (W/L) when 25 DEG C, output in 2 seconds.

By output characteristics evaluation result is shown in table 10." exporting within 2 seconds " in table 10 refers to defeated after electric discharge starts 2 seconds Out, the output referred to after electric discharge starts 5 seconds " is exported within 5 seconds ".

As shown in table 10, unrelated with the difference of temperature, the output of EB2 and the output phase of CB2 are higher than obvious.Equally, EB3 The output phase ratio of output and CB3, hence it is evident that high.

In addition, the battery output density of EB2 is obvious high compared with the battery output density of CB2.Equally, the battery of EB3 is defeated Density is obvious high compared with the battery output density of CB3 out.

Table 10

(evaluation example 11: low-temperature test)

Electrolyte E11, E13, E16, E19 are respectively put into container, filling non-active gas carries out closed.By they- 30 DEG C of refrigerator is taken care of 2 days.Each electrolyte is observed after keeping.Any electrolyte maintains liquid condition without solidification, The precipitation of salt is not observed.

(embodiment 1-1)

Following manufacture has used the non-aqueous electrolyte secondary battery of the embodiment 1-1 of electrolyte E8.Anode and non-aqueous solution electrolysis The anode of electrolitc secondary cell EB2 is carried out similarly manufacture.

It will be as 98 mass parts of natural graphite of negative electrode active material and as the SBR1 mass parts and CMC1 of binder Mass parts mixing.So that the mixture is scattered in suitable ion exchange water, makes slurry.Prepare 20 μm of thickness of copper foil as negative Electrode current collector.Using scraper, above-mentioned slurry is coated on the surface of the copper foil membranaceous.The copper foil for being coated with slurry it is dry and Water is removed, thereafter, pressurizes to copper foil, obtains binding element.By obtained binding element vacuum drier in 100 DEG C of heat dryings 6 Hour, obtain the copper foil for being formed with negative electrode active material layer.As cathode.

As separator, preparing experiment is with filter paper (filter paper Co., Ltd., Japan, cellulose system, 260 μm of thickness).

Separator is clamped with anode and cathode, polar plate group is made.Two one group of laminated film of the polar plate group is covered, it will After three sides are sealed, electrolyte E8 is injected to the laminated film taken the shape of a bag.Thereafter, it is sealed remaining on one side, thus It is hermetically sealed to four sides, polar plate group and electrolyte are by closed non-aqueous electrolyte secondary battery.Using the battery as implementation The non-aqueous electrolyte secondary battery of example 1-1.

(embodiment 1-2)

The non-aqueous electrolyte secondary battery of embodiment 1-2 except use electrolyte E4 as electrolyte in addition to, with embodiment 1-1 Non-aqueous electrolyte secondary battery it is identical.Electrolyte in the non-aqueous electrolyte secondary battery of embodiment 1-2 is as solvent Acetonitrile in dissolution as support salt (SO₂CF₃)₂Made of NLi (LiTFSA).The concentration of lithium salts contained by 1 liter of electrolyte is 4.2mol/L.In electrolyte, relative to 1 molecule of lithium salts, the acetonitrile containing 2 molecules.

(embodiment 1-3)

The non-aqueous electrolyte secondary battery of embodiment 1-3 except use electrolyte E11 as electrolyte in addition to, with embodiment 1- 1 non-aqueous electrolyte secondary battery is identical.Electrolyte in the non-aqueous electrolyte secondary battery of embodiment 1-3 is as solvent DMC in dissolution as support salt LiFSA made of.The concentration of lithium salts contained by 1 liter of electrolyte is 3.9mol/L.Electrolyte In, relative to 1 molecule of lithium salts, the DMC containing 2 molecules.

(embodiment 1-4)

The non-aqueous electrolyte secondary battery of embodiment 1-4 has used electrolyte E11.The nonaqueous electrolyte two of embodiment 1-4 Primary cell removes type, positive active material and the conductive auxiliary agent of electrolyte and the mixing ratio of binder, negative electrode active material and glues It is identical as the non-aqueous electrolyte secondary battery of embodiment 1-1 other than mixing ratio and the separator of tying agent.For anode, use NCM523 as a positive electrode active material, uses AB to use PVdF as binder as the conductive auxiliary agent of anode.Itself and implementation Example 1-1 is same.Their match ratio is NCM523:AB:PVdF=90:8:2.The unit plane of active material layer in anode Product weight is 5.5mg/cm², density 2.5g/cm³.It is also for embodiment 1-5~1-7 below and comparative example 1-2,1-3 Similarly.

For cathode, uses natural graphite as negative electrode active material, use SBR and CMC as the bonding material of cathode Material.In addition it is also same with embodiment 1-1.Their match ratio is natural graphite: SBR:CMC=98:1:1.In cathode Active material layer weight per unit area be 3.8mg/cm², density 1.1g/cm³.It is for embodiment 1-5~1- below 7 and comparative example 1-2,1-3 be also same.

As separator, 20 μm of thickness of cellulose non-woven fabrics has been used.

Electrolyte in the non-aqueous electrolyte secondary battery of embodiment 1-4 is that dissolution is used as branch in the DMC as solvent It holds made of the LiFSA of salt.The concentration of lithium salts contained by 1 liter of electrolyte is 3.9mol/L.In electrolyte, divide relative to lithium salts 1 Son, the DMC containing 2 molecules.

(embodiment 1-5)

The non-aqueous electrolyte secondary battery of embodiment 1-5 has used electrolyte E8.The nonaqueous electrolyte of embodiment 1-5 is secondary Battery except the mixing ratio of positive active material and conductive auxiliary agent and binder, the mixing ratio of negative electrode active material and binder and It is identical as the non-aqueous electrolyte secondary battery of embodiment 1-1 other than separator.It is NCM523:AB:PVdF=90 for anode: 8:2.It is natural graphite for cathode: SBR:CMC=98:1:1.As separator, used 20 μm of thickness of cellulose system without Woven fabric.

(embodiment 1-6)

The non-aqueous electrolyte secondary battery of embodiment 1-6 has used electrolyte E11.The nonaqueous electrolyte two of embodiment 1-6 Primary cell removes the binding material of type, positive active material and the conductive auxiliary agent of electrolyte and the mixing ratio of binder, cathode Type, other than the mixing ratio of negative electrode active material and binder and separator, the secondary electricity of nonaqueous electrolyte with embodiment 1-1 Pond is identical.It is NCM523:AB:PVdF=90:8:2 for anode.For cathode, use natural graphite as negative electrode active material Matter uses polyacrylic acid (PAA) as the binding material of cathode.Their match ratio is natural graphite: PAA=90:10.Make For separator, 20 μm of thickness of cellulose non-woven fabrics has been used.

(embodiment 1-7)

The non-aqueous electrolyte secondary battery of embodiment 1-7 has used electrolyte E8.The nonaqueous electrolyte of embodiment 1-7 is secondary Battery removes mixing ratio, the type of the binding material of cathode, negative electrode active of positive active material and conductive auxiliary agent and binder It is identical as the non-aqueous electrolyte secondary battery of embodiment 1-1 other than the mixing ratio and separator of substance and binder.For just Pole is NCM523:AB:PVdF=90:8:2.It is natural graphite for cathode: PAA=90:10.As separator, use 20 μm of thickness of cellulose non-woven fabrics.

(embodiment 1-8)

The non-aqueous electrolyte secondary battery of embodiment 1-8 has used electrolyte E13.The nonaqueous electrolyte two of embodiment 1-8 Primary cell except positive active material and conductive auxiliary agent mixing ratio, the type of the binding material of cathode, negative electrode active material with It is identical as the non-aqueous electrolyte secondary battery of embodiment 1-1 other than the mixing ratio and separator of binder.For anode, it is NCM523:AB:PVdF=90:8:2.It is natural graphite for cathode: SBR:CMC=98:1:1.As separator, use 20 μm of thickness of cellulose non-woven fabrics.

(comparative example 1-1)

The non-aqueous electrolyte secondary battery of comparative example 1-1 uses electrolyte C5 as electrolyte, in addition to this, with embodiment 1-1 is same.

(comparative example 1-2)

The non-aqueous electrolyte secondary battery of comparative example 1-2 has used electrolyte C5.The nonaqueous electrolyte of comparative example 1-2 is secondary Battery is except type, positive active material and the conductive auxiliary agent of electrolyte and mixing ratio, negative electrode active material and the bonding of binder It is identical as the non-aqueous electrolyte secondary battery of embodiment 1-1 other than the mixing ratio and separator of agent.It is NCM523 for anode: AB:PVdF=90:8:2.It is natural graphite for cathode: SBR:CMC=98:1:1.As separator, 20 μm of thickness have been used Cellulose non-woven fabrics.

(comparative example 1-3)

The non-aqueous electrolyte secondary battery of comparative example 1-3 has used electrolyte C5.The nonaqueous electrolyte of comparative example 1-3 is secondary Battery is except type, positive active material and the conductive auxiliary agent and the mixing ratio of binder of electrolyte, the binding material of cathode Non-aqueous electrolyte secondary battery other than type, the mixing ratio of negative electrode active material and binder and separator, with embodiment 1-1 It is identical.It is NCM523:AB:PVdF=90:8:2 for anode.It is natural graphite for cathode: PAA=90:10.As every Off member has used 20 μm of thickness of cellulose non-woven fabrics.

The battery of embodiment and comparative example is constituted shown in table 11.

Table 11

(evaluation example 12: the analysis containing S, O envelope)

Hereinafter, as needed, containing what the surface of the cathode in the non-aqueous electrolyte secondary battery of each embodiment was formed S, O envelope is referred to as cathode envelope containing S, O of each embodiment, by the cathode in the non-aqueous electrolyte secondary battery of each comparative example The envelope that is formed of surface be referred to as the cathode envelope of each comparative example.

In addition, as needed, the quilt that the surface of the anode in the non-aqueous electrolyte secondary battery of each embodiment is formed Film is referred to as anode envelope containing S, O of each embodiment, by the table of the anode in the non-aqueous electrolyte secondary battery of each comparative example The envelope that face is formed is referred to as the positive envelope of each comparative example.

(analysis of the cathode containing S, O envelope and cathode envelope)

100 times are repeated for the non-aqueous electrolyte secondary battery of embodiment 1-1, embodiment 1-2 and comparative example 1-1 to follow After ring charge and discharge, pass through x-ray photoelectron spectroscopy (X-ray Photoelectron under the discharge condition of voltage 3.0V Spectroscopy, XPS) carry out the analysis containing S, O envelope or envelope surface.As pre-treatment, processing below is carried out.It is first First, non-aqueous electrolyte secondary battery is disintegrated and takes out cathode, and the cathode is cleaned and dried, obtained as analysis object Cathode.Cleaning is carried out 3 times using DMC (dimethyl carbonate).In addition, from the disintegration of battery to the cathode that will be used as analysis object The whole processes for being transported to analytical equipment are to contact cathode with atmosphere under Ar compression ring border and carry out.To embodiment 1-1, Each non-aqueous electrolyte secondary battery of embodiment 1-2 and comparative example 1-1 carries out pre-treatment below, by an obtained cathode specimen into Row XPS analysis.As device, ULVAC-PHI company PHI5000VersaProbeII is used.X-ray source is monochrome AlK alpha ray (15kV, 10mA).By using the cathode of the embodiment 1-1 of XPS measurement, embodiment 1-2 containing the negative of S, O envelope and comparative example 1-1 The analysis result of pole envelope is shown in Figure 37~Figure 41.Specifically, Figure 37 is the analysis for carbon as a result, Figure 38 is to be directed to The analysis of fluorine element is as a result, Figure 39 is the analysis for nitrogen as a result, Figure 40 is the analysis for oxygen element as a result, Figure 41 is For the analysis result of element sulphur.

The electrolyte of the non-aqueous electrolyte secondary battery of embodiment 1-1 and the non-aqueous electrolyte secondary battery of embodiment 1-2 Electrolyte salt in contain element sulphur (S), oxygen element and nitrogen (N).In contrast, the nonaqueous electrolyte of comparative example 1-1 These elements are free of in the salt of the electrolyte of secondary cell.In addition, embodiment 1-1, embodiment 1-2 and comparative example 1-1's is non-aqueous The electrolyte of electrolyte secondary battery contains fluorine element (F), carbon (C) and oxygen element (O) in salt.

As shown in Figure 37~Figure 41, to the cathode of embodiment 1-1 containing the cathode of S, O envelope and embodiment 1-2 envelope containing S, O It is analyzed, as a result observe the existing peak (Figure 41) of display S and shows the existing peak (Figure 39) of N.That is, implementing Cathode envelope containing S, O containing the cathode of S, O envelope and embodiment 1-2 of example 1-1 contains S and N.But in the cathode of comparative example 1-1 These peaks are not found in the analysis result of envelope.That is, the cathode envelope of comparative example 1-1 is without containing more than detection limit Any of S and N of amount.It should be noted that cathode of the existing peak of display F, C and O in embodiment 1-1, embodiment 1-2 contains S, it is observed in whole analysis results of the cathode envelope of O envelope and comparative example 1-1.That is, embodiment 1-1, implementation The cathode of example 1-2 contains F, C and O containing the cathode envelope of S, O envelope and comparative example 1-1.

These elements are the ingredients from electrolyte.Especially S, O and F are ingredients contained by the metal salt of electrolyte, Specifically ingredient contained by the chemical structure of the anion of metal salt.Therefore, each cathode quilt containing S, O as knowen from these results Film and cathode envelope contain the ingredient of the chemical structure of the anion from metal salt (that is supporting salt).

The analysis result of element sulphur shown in Figure 41 (S) is parsed in more detail.For embodiment 1-1 and embodiment The analysis of 1-2 is as a result, carry out peak separation using Gauss/Lorentz mixed function.The parsing result of embodiment 1-1 is shown in figure 42, the parsing result of embodiment 1-2 is shown in Figure 43.

As shown in Figure 42 and Figure 43, cathode envelope containing S, O of embodiment 1-1 and 1-2 are analyzed, as a result 165~ 175eV nearby observes biggish peak (waveform).Moreover, the peak (waveform) near the 170eV is divided as shown in Figure 42 and Figure 43 From at 4 peaks.One of them is to indicate SO₂Peak near the existing 170eV of (S=O structure).According to the result, it may be said that What negative terminal surface was formed in non-aqueous electrolyte secondary battery of the invention has S=O structure containing S, O envelope.Moreover, it is contemplated that should As a result with above-mentioned XPS analysis result, thus it is speculated that S contained by the S=O structure containing S, O envelope be metal salt support salt yin from S contained by the chemical structure of son.

(S elemental ratio of the cathode containing S, O envelope)

XPS analysis based on above-mentioned cathode containing S, O envelope is as a result, the cathode for calculating embodiment 1-1 and embodiment 1-2 contains S, the ratio of S element when electric discharge in the cathode envelope of O envelope and comparative example 1-1.Specifically, to each cathode quilt containing S, O Film and cathode envelope calculate the element ratio of the S when summation of the peak intensity of S, N, F, C, O is set as 100%.Show the result in table 12。

Table 12

	Embodiment 1-1	Embodiment 1-2	Comparative example 1-1
				S elemental ratio (atom %)	10.4	3.7	0.0

As described above, the cathode envelope of comparative example 1-1 is without S more than detection limit, but from the cathode of embodiment 1-1 containing S, The cathode of O envelope and embodiment 1-2 envelope containing S, O detect S.In addition, the cathode of embodiment 1-1 contains S, O envelope and embodiment The cathode of 1-2 envelope containing S, O is compared, and more S are contained.It should be noted that not examined from the cathode of comparative example 1-1 containing S, O envelope S is measured, it can be said that be not from containing S contained by S, O envelope can not contained by positive active material for the cathode of each embodiment The impurity or other additives avoided, but the metal salt in electrolyte.

In addition, the cathode of embodiment 1-1 is 10.4 atom % containing the S elemental ratio in S, O envelope, embodiment 1-2's is negative Pole is 3.7 atom % containing the S elemental ratio in S, O envelope, therefore, in non-aqueous electrolyte secondary battery of the invention, cathode Containing the S elemental ratio in S, O envelope be 2.0 atom % or more, preferably 2.5 atom % or more, more preferably 3.0 atom % with On, further preferably 3.5 atom % or more.It should be noted that as described above S elemental ratio (atom %) refer to by S, N, F, C, the peak intensity ratio of the S when summation of the peak intensity of O is set as 100%.The upper limit value of the elemental ratio of S is not particularly limited, non- If it is required that, preferably 25 atom % or less.

(thickness of the cathode containing S, O envelope)

Prepare to become voltage after the non-aqueous electrolyte secondary battery of embodiment 1-1 being repeated 100 cycle charge-discharges The battery of the discharge condition of 3.0V becomes the battery of the charged state of voltage 4.1V with being repeated after 100 cycle charge-discharges, Method same as the pre-treatment of above-mentioned XPS analysis is used to obtain the cathode specimen as analysis object.By negative to what is obtained A pole specimen carries out FIB (focused ion beam: Focused Ion Beam) processing, and the STEM analysis for obtaining thickness 100nm or so is used A specimen.It should be noted that the pre-treatment as FIB processing, has been deposited Pt on cathode.Above process does not make cathode and atmosphere It is carried out under conditions of contact.

Using being accompanied with EDX (energy dispersion type X-ray spectrum: Energy Dispersive X-ray spectroscopy) The STEM (scanning transmission electron microscope: Scanning Transmission Electron Microscope) of device is analyzed A specimen is used in each STEM analysis.Show the result in Figure 44~Figure 47.Wherein Figure 44 is BF (bright-field: Bright-field)-STEM Image, Figure 45~Figure 47 are the element distribution images of viewing area identical with Figure 44 obtained using SETM-EDX.In addition, figure 45 be the analysis for C as a result, Figure 46 is the analysis for O as a result, Figure 47 is the analysis result for S.It should be noted that Figure 45 ~Figure 47 is the analysis result of the cathode in the non-aqueous electrolyte secondary battery of discharge condition.

As shown in figure 44, in the upper left quarter of STEM image, there are the parts of black.The part of the black comes to be processed in FIB Pre-treatment in the Pt that is deposited.In each STEM image, it can be seen in the part of the upside of the part (the referred to as portion Pt) from Pt Work is contaminated part after Pt vapor deposition.Therefore, in Figure 45~Figure 47, only the part of the downside in the portion Pt is studied.

As shown in figure 45, in the downside in the portion Pt, stratiform is presented in C.It is thought that the layer of the graphite as negative electrode active material Shape structure.In Figure 46, O is located at and the periphery of graphite and the comparable part of interlayer.In addition, in Figure 47 S also be located at it is outer with graphite Week and the comparable part of interlayer.Contain cathode envelope containing S, O of the S and O of S=O structure etc. in graphite by these results presumptions Surface and interlayer are formed.

Random selection 10 is in cathode envelope containing S, O that the surface of graphite is formed, and measures thickness of the cathode containing S, O envelope, Calculate the average value of measured value.Cathode in the non-aqueous electrolyte secondary battery of charged state is similarly analyzed, based on each Analysis is as a result, calculate the average value of thickness of the cathode containing S, O envelope formed on the surface of graphite.Show the result in table 13.

Table 13

As shown in table 13, thickness of the cathode containing S, O envelope increases after charging.By results presumption cathode envelope containing S, O It is middle to exist relative to fixed part existing for stable charge/discharge and with the adsorption section of charge and discharge increase and decrease.And, thus it is speculated that due to absorption Portion exists, and cathode thickness in charge and discharge containing S, O envelope increases and decreases.

(analysis of positive envelope)

Prepare to become voltage after the non-aqueous electrolyte secondary battery of embodiment 1-1 being repeated 3 cycle charge-discharges Battery after 3 cycle charge-discharges as the charged state of voltage 4.1V, repeatedly is repeated in the battery of the discharge condition of 3.0V After carrying out the battery after 100 cycle charge-discharges as the discharge condition of voltage 3.0V, 100 cycle charge-discharges being repeated at It is totally 4, battery of the charged state of voltage 4.1V.The non-aqueous electrolyte secondary battery of this 4 embodiment 1-1 is used respectively Method similar to the above obtains the anode as analysis object.Then XPS analysis is carried out to obtained each anode.By result It is shown in Figure 48 and Figure 49.It should be noted that Figure 48 is the analysis for oxygen element as a result, Figure 49 is the analysis knot for element sulphur Fruit.

As shown in Figure 48 and Figure 49, it is known that in addition the anode of embodiment 1-1 also contains S and O containing S, O envelope.In addition, due to Occurs the peak near 170eV in Figure 49, it is known that the anode of embodiment 1-1 contains containing S, O envelope and the cathode of embodiment 1-1 S, in addition O envelope similarly also has the S=O structure from electrolyte of the invention.

However, as shown in figure 48, the height at existing peak is reduced after circulation near 529eV.Think that the peak indicates The presence of O from positive active material, specifically, the photoelectricity excited in XPS analysis by the O atom in positive active material Son is detected by the envelope containing S, O.Since the peak is reduced after circulation, it is believed that containing S, O what positive electrode surface was formed The thickness of envelope increases as the cycle progresses.

In addition, as shown in Figure 48 and Figure 49, anode containing in S, O envelope O and S increase in electric discharge, when charging, is reduced.Root According to the result, it is believed that O and S enters and leaves the positive envelope containing S, O along with charge and discharge.And it thus deduces the anode in charge and discharge and contains S, the concentration of S, O in O envelope increase and decrease, or anode contains in S, O envelope also due to inhaling in the same manner as cathode is containing S, O envelope The presence in attached portion and increase and decrease thickness.

In addition, for the non-aqueous electrolyte secondary battery of embodiment 1-4, also by the positive quilt containing S, O containing S, O envelope and cathode Film carries out XPS analysis.

The non-aqueous electrolyte secondary battery of embodiment 1-4 is set to become 25 DEG C, using voltage range 3.0V~4.1V, with multiplying power 1C 500 circulation CC charge and discharge repeatedly.After 500 circulations, measured just under the discharge condition of 3.0V and the charged state of 4.0V XPS spectrum of the pole containing S, O envelope.In addition, to the discharge condition of the 3.0V before cyclic test (that is after first charge and discharge) The cathode of discharge condition of the cathode containing the 3.0V after S, O envelope and 500 circulations carry out the element based on XPS point containing S, O envelope Analysis, calculates the cathode containing S elemental ratio contained by S, O envelope.Anode envelope containing S, O of the embodiment 1-4 of XPS measurement will be utilized Analysis result be shown in Figure 50 and Figure 51.Specifically, Figure 50 is the analysis for element sulphur as a result, Figure 51 is for oxygen element Analysis result.In addition, the S elemental ratio (atom %) shown in table 14 of the cathode envelope of XPS measurement will be utilized.It should be noted that S Elemental ratio calculates in the same manner as above-mentioned " S elemental ratio of the cathode containing S, O envelope " one.

It is also another from the envelope containing S, O of the anode in the non-aqueous electrolyte secondary battery of embodiment 1-4 as shown in Figure 50 and Figure 51 The existing peak for indicating S is detected outside and indicates the existing peak of O.In addition, the peak of S and the peak of O increase in electric discharge, charge When reduce.According to this as a result, demonstrating anode has S=O structure containing S, O envelope, positive O and S containing in S, O envelope are adjoint to be filled Electric discharge enters and leaves the positive envelope containing S, O.

Table 14

	After first charge and discharge	After 500 circulations
			S elemental ratio (atom %)	3.1	3.8

In addition, as shown in table 14, the cathode of embodiment 1-4 follows after first charge and discharge, by 500 times containing S, O envelope After ring, the S containing 2.0 atom % or more.It can be seen from this result that the cathode in non-aqueous electrolyte secondary battery of the invention contains S, O envelope is in the S before recycling and after circulation containing 2.0 atom % or more.

The non-aqueous electrolyte secondary battery of embodiment 1-4~embodiment 1-7 and comparative example 1-2, comparative example 1-3 are carried out 60 DEG C of storages, 1 week high-temperature storage test, the anode of each embodiment after high-temperature storage test is contained containing S, O envelope and cathode S, the positive envelope and cathode envelope of O envelope and each comparative example are analyzed.Before high-temperature storage on-test, with multiplying power 0.33C carries out CC-CV from 3.0V and charges to 4.1V.On the basis of charging capacity at this time (SOC100), relative to benchmark CC After electric discharge 20% is partly adjusted to SOC80, start high-temperature storage test.CC-CV is carried out after high-temperature storage test with 1C to put Electricity is to 3.0V.Then, the anode after measurement electric discharge is containing S, O envelope and cathode containing S, O envelope and positive envelope and cathode envelope XPS spectrum.S, O envelope and comparative example 1-2 and ratio will be contained using embodiment 1-4~embodiment 1-7 anode of XPS measurement The analysis result of positive envelope compared with example 1-3 is shown in Figure 52~Figure 55.In addition, embodiment 1-4~implementation of XPS measurement will be utilized The cathode of example 1-7 is shown in Figure 56~figure containing the analysis result of the cathode envelope of S, O envelope and comparative example 1-2 and comparative example 1-3 52。

Specifically, Figure 52 be for embodiment 1-4, embodiment 1-5 anode containing S, O envelope and comparative example 1-2 just The analysis result of the element sulphur of pole envelope.Figure 53 is to be directed to the anode of embodiment 1-6, embodiment 1-7 containing S, O envelope and comparative example The analysis result of the element sulphur of the positive envelope of 1-3.Figure 54 is anode envelope containing S, O for embodiment 1-4, embodiment 1-5 With the analysis result of the oxygen element of the positive envelope of comparative example 1-2.Figure 55 be for embodiment 1-6, embodiment 1-7 anode contain S, the analysis result of the oxygen element of the positive envelope of O envelope and comparative example 1-3.In addition, Figure 56 is for embodiment 1-4, implements The cathode of example 1-5 is containing the analysis result of the element sulphur of the cathode envelope of S, O envelope and comparative example 1-2.Figure 57 is for embodiment 1-6, embodiment 1-7 cathode containing the analysis result of the element sulphur of the cathode envelope of S, O envelope and comparative example 1-3.Figure 58 is needle To the cathode of embodiment 1-4, embodiment 1-5 containing the analysis result of the oxygen element of the cathode envelope of S, O envelope and comparative example 1-2. Figure 59 is point of the cathode containing the oxygen element of the cathode envelope of S, O envelope and comparative example 1-3 for embodiment 1-6, embodiment 1-7 Analyse result.

As shown in Figure 52 and Figure 53, the nonaqueous electrolyte of the comparative example 1-2 and comparative example 1-3 of existing electrolyte have been used Embodiment 1-4~embodiment 1-7 of electrolyte of the invention has been used in contrast without S in the positive envelope of secondary cell Non-aqueous electrolyte secondary battery anode containing containing S in S, O envelope.In addition, as shown in Figure 54 and Figure 55, embodiment 1-4~ The anode of the non-aqueous electrolyte secondary battery of embodiment 1-7 contains in S, O envelope and contains O.In addition, as shown in Figure 52 and Figure 53, Detecting from the anode in embodiment 1-4~embodiment 1-7 non-aqueous electrolyte secondary battery containing S, O envelope indicates SO₂(S =O structure) existing 170eV near peak.As knowen from these results in non-aqueous electrolyte secondary battery of the invention, make When using organic solvent as electrolyte of AN, DMC, it is respectively formed stable anode envelope containing S, O containing S and O.In addition, by In the anode containing S, O envelope not by the species influence of negative electrode binder, it is believed that anode is not from containing the O in S, O envelope CMC.In addition, as shown in Figure 54 and Figure 55, when using DMC as the organic solvent of electrolyte, detects and near 530eV From the peak O of positive active material.It is therefore contemplated that when using DMC as the organic solvent of electrolyte, with phase the case where using AN Than the positive thickness containing S, O envelope is thinning.

Similarly, the cathode of embodiment 1-4~embodiment 1-7 non-aqueous electrolyte secondary battery is known by Figure 56~Figure 59 The envelope containing S, O also contains S and O, they form S=O structure and come from electrolyte.And know use AN, DMC as electrolysis Cathode envelope containing S, O is respectively formed when the organic solvent of liquid.

Above-mentioned high temperature storage is measured to the non-aqueous electrolyte secondary battery of embodiment 1-4, embodiment 1-5 and comparative example 1-2 XPS spectrum of each cathode containing S, O envelope and cathode envelope after hiding test and electric discharge, calculates embodiment 1-4, embodiment 1-5 Cathode envelope of the cathode containing S, O envelope and comparative example 1-2 in electric discharge when S element ratio.Specifically, to each cathode The element ratio of the S when summation of the peak intensity of S, N, F, C, O is set as 100% is calculated containing S, O envelope or cathode envelope.By result Shown in table 15.

Table 15

	Embodiment 1-4	Embodiment 1-5	Comparative example 1-2
				S elemental ratio (atom %)	4.2	6.4	0.0

As shown in Table 15, the cathode envelope of comparative example 1-2 is without S more than detection limit, but from embodiment 1-4 and embodiment The cathode of 1-5 envelope containing S, O detects S.In addition, cathode of the cathode of embodiment 1-5 containing S, O envelope and embodiment 1-4 contains S, O Envelope is compared, and more S are contained.Even if in addition, it can be seen from this result that cathode is containing the S element in S, O envelope after high-temperature storage Ratio is also 2.0 atom % or more.

(evaluation example 13: the internal resistance of battery)

Prepare the non-aqueous electrolyte secondary battery of embodiment 1-4, embodiment 1-5, embodiment 1-8 and comparative example 1-2, evaluation The internal resistance of battery.

To each non-aqueous electrolyte secondary battery of embodiment 1-4, embodiment 1-5, embodiment 1-8 and comparative example 1-2, in room CC charge and discharge (that is constant current charge and discharge) are repeated in temperature, the range of 3.0V~4.1V (vs.Li benchmark).Then, AC impedance after measuring first charge and discharge and the AC impedance after 100 circulations.It is bent based on obtained complex impedance plane Line parses the reaction resistance of electrolyte, cathode and anode respectively.As shown in figure 60, in complex impedance plane curve, it is seen that two Circular arc.The circular arc in left side (i.e. the small side of the real part of complex impedance) in figure is known as the 1st circular arc.The circular arc on right side in figure is known as 2nd circular arc.The reaction resistance that cathode is parsed according to the size of the 1st circular arc, according to the reaction electricity of the size of the 2nd circular arc parsing anode Resistance.According to the resistance with the Curve Resolution electrolyte of the leftmost side in Figure 60 of the 1st circular sliding slopes.By parsing result 6 He shown in table 1 Table 17.It should be noted that table 16 shows the reaction electricity of the resistance (so-called solution resistance) of the electrolyte after first charge and discharge, cathode Resistance, positive reaction resistance, table 17 show each resistance after 100 circulations.

Table 16

The initial AC resistance > unit of <: Ω

Table 17

AC resistance > unit after < 100 times circulations: Ω

Negative reaction resistance as shown in table 16 and table 17, in each non-aqueous electrolyte secondary battery, after 100 circulations Has the tendency that reduction compared with each resistance after first charge and discharge with positive reaction resistance.Moreover, by 100 shown in table 17 After secondary circulation, the negative reaction resistance of the non-aqueous electrolyte secondary battery of each embodiment and positive reaction resistance are than comparative example 1-2 Non-aqueous electrolyte secondary battery negative reaction resistance it is low with positive reaction resistance.

As described above, the non-aqueous electrolyte secondary battery of embodiment 1-4, embodiment 1-5 and embodiment 1-8 have used this hair Bright electrolyte forms the envelope containing S, O from electrolyte of the invention on the surface of cathode and anode.In contrast, exist Not in the non-aqueous electrolyte secondary battery using the comparative example 1-2 of electrolyte of the invention, do not have on the surface of cathode and anode It to form this and contain S, O envelope.Moreover, as shown in table 17, the negative reaction electricity of embodiment 1-4, embodiment 1-5 and embodiment 1-8 Resistance and positive reaction resistance are lower than the non-aqueous electrolyte secondary battery of comparative example 1-2.Thus, thus it is speculated that in each embodiment, due to coming From the presence containing S, O envelope of electrolyte of the invention, reduce negative reaction resistance and positive reaction resistance.

It should be noted that the solution resistance of the electrolyte in the non-aqueous electrolyte secondary battery of embodiment 1-5 and comparative example 1-2 Almost the same, the solution resistance of the electrolyte in the non-aqueous electrolyte secondary battery of embodiment 1-4 and embodiment 1-8 compares embodiment 1-5 and comparative example 1-2 high.In addition, the solution resistance of each electrolyte in each non-aqueous electrolyte secondary battery is in first charge and discharge Afterwards and by 100 times circulation after it is also almost the same.It is therefore contemplated that there is no the durable deteriorations of each electrolyte, it is believed that above-mentioned The difference of the negative reaction resistance and positive reaction resistance that generate in comparative example and embodiment is unrelated with the durable deterioration of electrolyte, and It is to be generated by electrode itself.

The internal resistance of non-aqueous electrolyte secondary battery can be by the solution resistance of electrolyte, the reaction resistance of cathode and just The reaction resistance comprehensive descision of pole.It is based on table 16 and table 17 as a result, from the internal resistance for inhibiting non-aqueous electrolyte secondary battery From the viewpoint of increase, it may be said that the durability of the non-aqueous electrolyte secondary battery of embodiment 1-4 and embodiment 1-8 is especially excellent It is different, the then excellent in te pins of durability of the non-aqueous electrolyte secondary battery of embodiment 1-5.

(evaluation example 14: the cyclic durability of battery)

To each non-aqueous electrolyte secondary battery of embodiment 1-4, embodiment 1-5, embodiment 1-8 and comparative example 1-2, in room CC charge and discharge are repeated in temperature, the range of 3.0V~4.1V (vs.Li benchmark), measure discharge capacity when first charge and discharge, 100 Discharge capacity when discharge capacity when secondary circulation and 500 circulations.Moreover, each nonaqueous electrolyte two when by first charge and discharge The capacity of primary cell is set as 100%, the appearance of each non-aqueous electrolyte secondary battery when calculating 100 circulations and when 500 times recycle It measures sustainment rate (%).Show the result in table 18.

Table 18

As shown in table 18, the non-aqueous electrolyte secondary battery of embodiment 1-4, embodiment 1-5 and embodiment 1-8 are although be free of The EC of material as SEI, but show and tieed up with the same capacity of the non-aqueous electrolyte secondary battery of the comparative example 1-2 containing EC Holdup.It is thought that due to existing in the anode and cathode in the non-aqueous electrolyte secondary battery of each embodiment from of the invention The envelope containing S, O of electrolyte.Moreover, the non-aqueous electrolyte secondary battery of embodiment 1-4 is especially when by 500 circulations Show high capacity maintenance rate, durability is especially excellent.According to the result, it may be said that when selecting DMC as organic solvent, Compared with the case where selecting AN, durability is further increased.

(evaluation example 15: high-temperature storage test)

The non-aqueous electrolyte secondary battery of embodiment 1-4, embodiment 1-5 and comparative example 1-2 store 1 week at 60 DEG C High-temperature storage test.Before high-temperature storage on-test, 4.1V is charged to from 3.0V CC-CV (constant-current constant-voltage). On the basis of charging capacity at this time (SOC100), after being adjusted to SOC80 relative to 20% part of benchmark CC electric discharge, start High-temperature storage test.CC-CV is carried out with 1C after high-temperature storage test and is discharged to 3.0V.By at this time discharge capacity and storage before The ratio between SOC80 capacity, residual capacity is calculated as following formula.Show the result in table 19.

Residual capacity=100 × (the CC-CV discharge capacity after storage)/(the SOC80 capacity before storage)

Table 19

Non- water power of the residual capacity of the non-aqueous electrolyte secondary battery of embodiment 1-4 and embodiment 1-5 than comparative example 1-2 The residual capacity for solving electrolitc secondary cell is big.According to the result, it may be said that being formed in from electrolyte of the invention is positive and negative The envelope containing S, O of pole also contributes to residual capacity increase.

(evaluation example 16: rate capability characteristic)

Rate capability with the non-aqueous electrolyte secondary battery of the following method evaluation embodiment 1-1 and comparative example 1-1 is special Property.The capacity of each battery is adjusted to 160mAh/g.Evaluation condition be to each non-aqueous electrolyte secondary battery, with 0.1C, The speed of 0.2C, 0.5C, 1C, 2C are discharged after being charged, and measure capacity (the electric discharge appearance of the working electrode under each speed Amount).Discharge capacity after 0.1C is discharged and after 1C electric discharge is shown in table 20.It should be noted that discharge capacity shown in table 20 is The capacity of quality (g) relative to positive active material.

Table 20

	Embodiment 1-1	Comparative example 1-1
			0.1C capacity (mAh/g)	158.3	158.2
1.0C capacity (mAh/g)	137.5	125.0

As shown in table 20, when the velocity of discharge is slow (0.1C), in the non-aqueous electrolyte secondary battery and comparative example of embodiment 1-1 Almost without the difference of discharge capacity between the non-aqueous electrolyte secondary battery of 1-1.But the velocity of discharge it is fast when (1.0C), it is real The electric discharge for applying non-aqueous electrolyte secondary battery of the discharge capacity than comparative example 1-1 of the non-aqueous electrolyte secondary battery of a 1-1 is held Amount is big.The result demonstrates the rate capability excellent of non-aqueous electrolyte secondary battery of the invention.As noted above it is believed that this It is since the electrolyte in non-aqueous electrolyte secondary battery of the invention is different from existing electrolyte, in addition, of the invention The cathode of non-aqueous electrolyte secondary battery and/or anode formed containing S, O envelope also with existing difference.

(output characteristics evaluation when evaluation 17:0 DEG C of example, SOC20%)

The output characteristics of the non-aqueous electrolyte secondary battery of the above embodiments 1-1 and comparative example 1-1 is evaluated.It comments Valence condition is 20%, 0 DEG C of charged state (SOC), using voltage range 3V-4.2V, capacity 13.5mAh.SOC20%, 0 DEG C for example It is the region that the output characteristics as in the case where refrigerating chamber etc. uses is not easy to embody.Embodiment 1-1's and comparative example 1-1 is non-aqueous The evaluation of the output characteristics of electrolyte secondary battery is to carry out output in 2 seconds and output in 5 seconds each 3 times respectively.By commenting for output characteristics Valence result is shown in table 21." exporting within 2 seconds " in table 21 refers to the output after electric discharge starts 2 seconds, and " exporting within 5 seconds " refers to and discharging Output after starting 5 seconds.It is also same in aftermentioned 22~table of table 23.

Table 21

Output characteristics (0 DEG C, SOC20%)

As shown in table 21, output and comparative example of the non-aqueous electrolyte secondary battery of embodiment 1-1 in 0 DEG C, SOC20% The output phase ratio of the non-aqueous electrolyte secondary battery of 1-1 is 1.2 times high~1.3 times.

(output characteristics evaluation when evaluation 18:25 DEG C of example, SOC20%)

20%, 25 DEG C of charged state (SOC), using voltage range 3V -4.2V, capacity 13.5mAh under conditions of evaluate The output characteristics of the lithium ion battery of embodiment 1-1 and comparative example 1-1.The nonaqueous electrolyte two of embodiment 1-1 and comparative example 1-1 The evaluation of the output characteristics of primary cell is to carry out output in 2 seconds and output in 5 seconds each 3 times respectively.Show the results of the evaluation table 22.

Table 22

Output characteristics (25 DEG C, SOC20%)

As shown in table 22, output of the non-aqueous electrolyte secondary battery of embodiment 1-1 in 25 DEG C, SOC20% is compared with The output phase ratio of the non-aqueous electrolyte secondary battery of example 1-1 is 1.2 times high~1.3 times.

(evaluation example 19: influence of the temperature to output characteristics)

In addition, analyzing temperature when measurement to the non-aqueous electrolyte secondary battery of the above embodiments 1-1 and comparative example 1-1 Output characteristics influence.It is measured at 0 DEG C and 25 DEG C, in the measurement at any temperature, evaluation condition is charged state (SOC) 20% voltage range 3V -4.2V, capacity 13.5mAh, are used.The output phase at 0 DEG C is found out for the output at 25 DEG C Ratio (0 DEG C output/25 DEG C output).The results are shown in tables 23.

Table 23

/ 25 DEG C of outputs of 0 DEG C of output

	Embodiment 1-1	Comparative example 1-1
			It exports within 2 seconds	0.26	0.27
It exports within 5 seconds	0.26	0.26

As shown in table 23, for the non-aqueous electrolyte secondary battery of embodiment 1-1, output in 2 seconds and 0 DEG C in output in 5 seconds Under output phase be nonaqueous electrolyte two with comparative example 1-1 for the ratio (0 DEG C output/25 DEG C output) of the output at 25 DEG C Primary cell equal extent, it is known that the non-aqueous electrolyte secondary battery of embodiment 1-1 can be with the nonaqueous electrolyte two of comparative example 1-1 Primary cell equally inhibits the output under low temperature to reduce.

(evaluation example 20: thermal stability)

With the following method evaluation embodiment 1-1, comparative example 1-1 non-aqueous electrolyte secondary battery electrolyte relative to The thermal stability of the anode of charged state.

It is under the conditions of end of charge voltage 4.2V, constant-current constant-voltage that non-aqueous electrolyte secondary battery is fully charged. Non-aqueous electrolyte secondary battery after will be filled with electricity disintegrates, and takes out anode.The positive electrode active material layer 3mg that will be obtained from the anode It is put into the pot of stainless steel with 1.8 μ L of electrolyte, the closed pot.Using closed pot, under nitrogen environment, with heating rate 20 DEG C/condition of min carries out differential scanning calorimetric analysis, observe DSC curve.As differential scanning calorimetry measurement device, use Rigaku DSC8230.By the positive electrode active material layer of the charged state of the non-aqueous electrolyte secondary battery of embodiment 1-1 and electricity DSC chart when solution liquid coexists is shown in Figure 61.In addition, by the charged state of the non-aqueous electrolyte secondary battery of comparative example 1-1 DSC chart when positive electrode active material layer and coexistent electrolyte solution is shown in Figure 62.

By the result of Figure 61 and Figure 62 it is found that the charged state in the non-aqueous electrolyte secondary battery of embodiment 1-1 just Almost without heat absorption and exothermic peak is observed in DSC curve when pole and coexistent electrolyte solution, in contrast, comparative example 1-1's The anode of the charged state of non-aqueous electrolyte secondary battery is nearby observed with DSC curve when coexistent electrolyte solution at 300 DEG C Exothermic peak.Infer that the exothermic peak is to react resulting with electrolyte by positive active material.

Used as knowen from these results the non-aqueous electrolyte secondary battery of electrolyte of the invention with used it is existing The non-aqueous electrolyte secondary battery of electrolyte compares, reactive low, the excellent heat stability of positive active material and electrolyte.

However, as noted above it is believed that imide salts easily corrode aluminium collector.When in the past, using aluminium collector, for The aluminium collector formed for inhibits corrosion protect envelope purpose, it is believed that a part of the metal salt of electrolyte need using LiPF₆Equal lithium salts.Such as in the embodiment of Japanese Unexamined Patent Publication 2013-145732, having cooperated in the electrolytic solution is the 4 of imide salts Times or so LiPF₆.In contrast, as follows, the not perishable aluminium of electrolyte of the invention.Therefore, non-water power of the invention It solves and preferably uses aluminium collector in electrolitc secondary cell.

(dissolution of evaluation example 21:Al confirms I)

(EB4)

Following manufacture has used the non-aqueous electrolyte secondary battery of electrolyte E8.

By diameter 13.82mm, area 1.5cm², 20 μm of thickness aluminium foil (JIS A1000) be used as working electrode, to electricity Extremely metal Li.Separator uses 400 μm of thickness of Whatman glass fiber filter paper: model 1825-055.

By working electrode, battery case (precious Izumi Ltd. CR2032 is housed in the electrolyte of electrode, separator and E8 Type button cell box) in obtain non-aqueous electrolyte secondary battery.

To EB4, the scanning of 10 sublinears is repeated in the range of 3.1V~4.6V (vs.Li benchmark) with the speed of 1mV/s Voltammetric determination (so-called LSV), observes the variation of electric current and electrode potential at this time.It will indicate the 1st time, the 2nd time, the 3rd of EB4 The relationship of the electric current and electrode potential of secondary charge and discharge is illustrated in Figure 63.

The working electrode known to Figure 63 is in the EB4 of Al, in 4.0V almost without discovery electric current, in the of short duration increasing of 4.3V electric current Greatly a bit, but thereafter significantly increase up to 4.6V does not see.In addition, becoming as the magnitude of current repeatedly of charge and discharge is reduced In stable state.

According to the above results, it is believed that the nonaqueous electrolyte two of aluminium collector is used using electrolyte of the invention and anode Even if primary cell is also not susceptible to the dissolution of Al under high potential.The reasons why being not susceptible to the dissolution of Al is still not clear, but speculates May be electrolyte of the invention compared with existing electrolyte the type of metal salt and organic solvent, there are environment and metal salt Concentration is different, and compared with existing electrolyte, Al is low to the dissolubility of electrolyte of the invention.

(evaluation example 22: being evaluated with the cyclic voltammetry of work electrode A l)

(EB5)

Electrolyte E8 is replaced in addition to this to get similarly non-aqueous electrolyte secondary battery with EB4 using electrolyte E11 EB5。

(EB6)

Electrolyte E8 is replaced in addition to this to get similarly non-aqueous electrolyte secondary battery with EB4 using electrolyte E16 EB6。

(EB7)

Electrolyte E8 is replaced in addition to this to get similarly non-aqueous electrolyte secondary battery with EB4 using electrolyte E19 EB7。

(EB8)

Electrolyte E8 is replaced in addition to this to get similarly non-aqueous electrolyte secondary battery with EB4 using electrolyte E13 EB8。

(CB4)

Electrolyte E8 is replaced in addition to this to get similarly non-aqueous electrolyte secondary battery with EB4 using electrolyte C5 CB4。

(CB5)

Electrolyte E8 is replaced in addition to this to get similarly non-aqueous electrolyte secondary battery with EB4 using electrolyte C6 CB5。

Non-aqueous electrolyte secondary battery EB4~EB7 and CB4 follow for 5 times under conditions of 3.1V~4.6V, 1mV/s The cyclic voltammetry of ring is evaluated, and thereafter, the cyclic voltammetry that 5 circulations are carried out under conditions of 3.1V~5.1V, 1mV/s is commented Valence.

In addition, the circulation of 10 circulations is carried out under conditions of 3.0V~4.5V, 1mV/s to half-cell EB5, EB8 and CB5 Voltammetry evaluation carries out the cyclic voltammetry evaluation of 10 circulations thereafter under conditions of 3.0V~5.0V, 1mV/s.

The curve for indicating the relationship of the current potential for being directed to EB4~EB7 and CB4 and response current is shown in Figure 64~Figure 72.Separately Outside, the curve for indicating the relationship of the current potential for being directed to EB5, EB8 and CB5 and response current is shown in Figure 73~Figure 78.

Known to Figure 72 in CB4, after 2 circulations, also there is electric current flowing from 3.1V to 4.6V, it is electric with height is become Position electric current increases.In addition, by being also in CB5 known to Figure 77 and Figure 78 likewise, after 2 circulations, from 3.0V to 4.5V Also there is electric current flowing, increase with high-potential current is become.Infer that the electric current is to be corroded by the aluminium of working electrode and generated The oxidation current of Al.

On the other hand, known to Figure 64~Figure 71 in EB4~EB7, after 2 circulations, from 3.1V to 4.6V almost There is no electric current flowing.A little increase of electric current is observed as current potential rises in 4.3V or more, but with iterative cycles, electric current Amount is reduced, and tend towards stability state.In especially EB5~EB7, the obvious of electric current was not observed before the 5.1V for high potential Increase, also, with the reduction for being repeatedly observed the magnitude of current of circulation.

In addition, by being also in EB5 and EB8 known to Figure 73~Figure 76 likewise, after 2 circulations, from 3.0V to 4.5V is almost without electric current flowing.Especially the 3rd time circulation after before reaching 4.5V electric current almost without increase.And And in EB8, though the increase of electric current is seen after the 4.5V for high potential, its current value later with the 4.5V in CB5 Compared to being very small value.It is same with EB5~EB7 until reaching 5.0V almost without the increase of electric current after 4.5V in EB5 Sample, with the reduction for being repeatedly observed the magnitude of current of circulation.

The result evaluated according to cyclic voltammetry, it may be said that even if in the case where being more than the high condition of 5V, electrolyte E8, E11, E16 and E19 are also low to the corrosivity of aluminium.That is, it can be said that electrolyte E8, E11, E16 and E19 use collector etc. It is preferred electrolyte for the battery of aluminium.

(dissolution of evaluation example 23:Al confirms II)

The non-aqueous electrolyte secondary battery of embodiment 1-1, embodiment 1-2 and comparative example 1-1 is set to use voltage range 3V ~4.2V is repeated 100 charge and discharge with multiplying power 1C, disintegrates after charge and discharge 100 times, takes out cathode.With ICP (inductance coupling Close plasma) measurement of emission spectrographic analysis device from anode dissolution to electrolyte is deposited in the Al amount on the surface of cathode.It will Measurement result is shown in table 24.The Al amount (%) of table 24 is that the quality of the Al of every 1g negative electrode active material layer is indicated with %, Al amount (μ G/ piece) indicate every 1 negative electrode active material layer Al quality (μ g), utilize Al amount (%) ÷ 100 × each negative electrode active material The calculating formula of quality=Al amount (μ g/ piece) of 1, layer is calculated.

Table 24

	Al amount (%)	Al amount (μ g/ piece)
			Embodiment 1-1	0.00480	11.183
Embodiment 1-2	0.00585	13.634
			Comparative example 1-1	0.03276	76.331

The secondary electricity of nonaqueous electrolyte of the non-aqueous electrolyte secondary battery of embodiment 1-1 and embodiment 1-2 and comparative example 1-1 Pond is compared, and the Al amount for being deposited in negative terminal surface is few very much.It follows that used electrolyte of the invention embodiment 1-1 and The non-aqueous electrolyte secondary battery of embodiment 1-2 and the nonaqueous electrolyte for the comparative example 1-1 for having used existing electrolyte are secondary Battery compares the dissolution for the collector for inhibiting Al from anode.

(surface analysis of evaluation example 24:Al collector)

Make the non-aqueous electrolyte secondary battery of embodiment 1-1 and embodiment 1-2 using voltage range 3V~4.2V, with again 100 charge and discharge are repeated in rate 1C, disintegrate after charge and discharge 100 times, take out the aluminium foil as positive collector respectively, use The surface of dimethyl carbonate cleaning aluminium foil.

Side sputters the aluminium foil to the non-aqueous electrolyte secondary battery of embodiment 1-1 and embodiment 1-2 after cleaning by Ar Surface be etched side and carry out surface analysis with X-ray photoelectron spectroscopy (XPS).By embodiment 1-1's and embodiment 1-2 The surface analysis result of aluminium foil after the charge and discharge of non-aqueous electrolyte secondary battery is shown in Figure 79 and Figure 80.

Comparison diagram 79 and Figure 80, it is known that after the charge and discharge of the non-aqueous electrolyte secondary battery of embodiment 1-1 and embodiment 1-2 The aluminium foil as anode collector surface analysis the result is that the two is almost the same, illustrate content below.In aluminium foil Surface, the chemical state of the Al of most surface is AlF₃.If etching aluminium foil in depth direction, the peak of Al, O, F are detected. In the position for carrying out 1 time~3 times etchings to aluminium foil from surface, the chemical state of Al is the combined state of Al-F key and Al-O key. From 4 etchings (with SiO if further etching₂Conversion depth be about 25nm) position start O, F peak disappear, only observe To the peak of Al.It should be noted that in the peak position Al, 76.3eV observes AlF in XPS determination data₃, seen in the peak position Al 73eV Pure Al is observed, and for the combined state of Al-F key and Al-O key, in the peak position Al, 74eV~76.3eV is observed.Figure 79 and figure Dotted line shown in 80 indicates AlF₃、Al、Al₂O₃Respective representativeness peak position.

According to the above results, it is able to confirm that the aluminium foil of the non-aqueous electrolyte secondary battery after charge and discharge of the invention Surface forms Al-F key and (is speculated as AlF in the thickness of depth direction about 25nm₃) layer and Al-F key (be speculated as AlF₃) (Al is speculated as with Al-O key₂O₃) mixing layer.

That is, it is known that in the non-aqueous electrolyte secondary battery of the invention that positive electrode collector has used aluminium foil, i.e., Just it can also be formed in the most surface of aluminium foil after charge and discharge using electrolyte of the invention and AlF (is speculated as by Al-F key₃) constitute Passivating film.

It is constituted known to evaluation example 21~evaluation example 24 result in combination electrolyte of the invention and by aluminum or aluminum alloy Anode collector non-aqueous electrolyte secondary battery in, by charge and discharge positive collector surface formed passivation Film, even if also, also inhibiting Al from the dissolution of positive collector under high potential state.

(evaluation example 25: anode is containing S, O by film analysis)

Utilize TOF-SIMS (Time-of-Flight Secondary Ion Mass Spectrometry: flight time Type secondary ion mass spectrometry), the positive structural information containing each molecule contained by S, O envelope of analysis embodiment 1-4.

By the non-aqueous electrolyte secondary battery of embodiment 1-4 after 25 DEG C of progress, 3 cycle charge-discharges, in 3V discharge condition Anode is taken out in lower disintegration.Additionally, by the non-aqueous electrolyte secondary battery of embodiment 1-4 in 25 DEG C of progress, 500 cycle charge discharges After electricity, disintegrates under 3V discharge condition and take out anode.And then additionally, the non-aqueous electrolyte secondary battery of embodiment 1-4 is existed It after 25 DEG C of progress, 3 cycle charge-discharges, is placed one month at 60 DEG C, disintegrates under 3V discharge condition and take out anode.It will be each with DMC Anode cleaning 3 times, obtains the anode of analysis.It should be noted that forming the positive envelope containing S, O in the anode, pass through below point Analysis, anode is analyzed containing the structural information of molecule contained by S, O envelope.

It is analyzed using each anode of the TOF-SIMS to analysis.As mass spectrograph, using time-of-flight type it is secondary from Sub- mass spectrograph measures positive secondary ion and negative secondary ion.Use Bi as primary ion source, an acceleration voltage is 25kV. As plasma sputter source, use Ar-GCIB (Ar1500).Measurement result is shown in 25~table of table 27.It should be noted that in table 26 The cation intensity (relative value) of each fragment is that the summation of the cation intensity for the whole fragments that will test is set as 100% phase To value.Similarly, the anion intensity (relative value) for each fragment that table 27 is recorded is the anion for the whole fragments that will test The summation of intensity is set as 100% relative value.

Table 25

(the main fragment detected)

Table 26

(cation analysis result)

Table 27

(anion analysis result)

As shown in Table 25, it is inferred as what the fragment of the solvent from electrolyte was detected only as positive secondary ion C₃H₃And C₄H₃.It is and above-mentioned in addition, the fragment for being inferred as the salt from electrolyte is detected mainly as negative secondary ion Fragment from solvent is compared, and ionic strength is big.In addition, the fragment containing Li is detected mainly as positive secondary ion, contain There is the ionic strength of the fragment of Li to account for very big ratio in positive secondary ion and negative secondary ion.

Thus speculate that the principal component of the invention containing S, O envelope is the ingredient of the metal salt contained by the electrolyte, and this The envelope containing S, O of invention contains a large amount of Li.

In addition, as shown in Table 25, as the fragment from salt is inferred as, also detecting SNO₂、SFO₂、S₂F₂NO₄Deng.They S=O structure is all had, and is the structure that N, F are bonded with S.That is, of the invention containing in S, O envelope, S not only with O shape At double bond, can also obtain as SNO₂、SFO₂、S₂F₂NO₄Deng the structure being bonded in this way with other elements.Therefore, it can be said that this As long as invention at least has S=O structure containing S, O envelope, S contained by S=O structure can be bonded with other elements. It should be noted that certainly, it is of the invention to contain the S and O for not forming S=O structure containing S, O envelope.

However, containing to be used as has in the electrolyte of the Japanese Unexamined Patent Publication 2013-145732 as escribed above existing type introduced The EC of solvent, the LiPF as metal salt₆In the existing electrolyte of the LiFSA as additive, S is introduced into organic solvent Decomposition product.Therefore, it is considered that S is in cathode envelope and/or positive envelope with C_pH_qS (p, q are respectively independent integer) plasma Form exist.In contrast, as shown in 25~table of table 27, the fragment containing S detected from the envelope of the invention containing S, O is not It is C_pH_qS fragment, based on the fragment for reflecting anion structure.This also indicate that it is of the invention containing S, O envelope with existing non- The envelope formed in Water-Electrolyte secondary cell is fundamentally different.

(other mode I)

Battery behavior is evaluated as follows to the non-aqueous electrolyte secondary battery for having used electrolyte of the invention.

(EB9)

It will be as 10 μm of average grain diameter of 90 mass parts of graphite of active material and as the Kynoar 10 of binder Mass parts mixing.So that the mixture is scattered in suitable n-methyl-2-pyrrolidone, makes slurry.Prepare 20 μm of thickness of copper Foil is as collector.Using scraper, above-mentioned slurry is coated on the surface of the copper foil membranaceous.The copper foil for being coated with slurry is dry It is dry and remove n-methyl-2-pyrrolidone, thereafter, pressurizes to copper foil, obtain binding element.Obtained binding element is dried in vacuo Machine 120 DEG C heat drying 6 hours, obtain the copper foil for being formed with active material layer.As working electrode.It should be noted that Every 1cm²The quality of the active material of copper foil is 1.48mg.In addition, the density of graphite and Kynoar before pressurization is 0.68g/cm³, the density of the active material layer after pressurization is 1.025g/cm³。

It is metal Li to electrode.

By working electrode, to electrode, be clipped in 400 μm of thickness of Whatman glass fibers as separator between the two Dimension filter paper and electrolyte E8 are housed in the battery case (precious Izumi Ltd. CR2032 type button cell box) of diameter 13.82mm Obtain non-aqueous electrolyte secondary battery EB9.

(EB10)

Using electrolyte E11, in addition to this, with method same as EB9, non-aqueous electrolyte secondary battery EB10 is obtained.

(EB11)

Using electrolyte E16, in addition to this, with method same as EB9, non-aqueous electrolyte secondary battery EB11 is obtained.

(EB12)

Using electrolyte E19, in addition to this, with method same as EB9, non-aqueous electrolyte secondary battery EB12 is obtained.

(CB6)

Using electrolyte C5, in addition to this, with method same as EB9, non-aqueous electrolyte secondary battery CB6 is obtained.

(evaluation example 26: multiplying power property)

It is tested with multiplying power property of the following method to EB9~EB12, CB6.With 0.1C, 0.2C, 0.5C, 1C, 2C Multiplying power is discharged after charging to each non-aqueous electrolyte secondary battery, and the capacity for measuring the working electrode under each speed (is put Capacitance).It should be noted that 1C refers to the current value needed for being kept battery fully charged in 1 hour at a certain current or being discharged.Separately Outside, description here is will to regard cathode as to electrode, regards working electrode as anode.Calculate capacity under other multiplying powers relative to The ratio (multiplying power property) of the capacity of working electrode under 0.1C multiplying power.Show the result in table 28.

Table 28

EB9, EB10, EB11, EB12 are demonstrated under the multiplying power of 0.2C, 0.5C, 1C, compared with CB6, it is suppressed that capacity Reduce, even and if then EB9, EB10 under the multiplying power of 2C compared with CB6, also inhibit capacity reduction, it is shown that excellent times Rate characteristic.

(evaluation example 27: capacity maintenance rate)

It is tested with capacity maintenance rate of the following method to EB9~EB12, CB6.

3 following charge and discharge cycles are carried out to each non-aqueous electrolyte secondary battery with charge-discharge magnification 0.1C, that is, at 25 DEG C CC charging (constant current charging) is carried out until voltage reaches 2.0V, then carries out CC electric discharge (constant current electric discharge) until voltage reaches To the charge and discharge cycles of the 2.0V-0.01V of 0.01V.Thereafter, each charge and discharge is directed to by the sequence of 0.2C, 0.5C, 1C, 2C, 5C, 10C Electric multiplying power respectively carries out the charge and discharge of 3 circulations, finally with the charge and discharge of 0.1C 3 circulations of progress.Each secondary electricity of nonaqueous electrolyte The capacity maintenance rate (%) in pond is found out using following formula.

Capacity maintenance rate (%)=B/A × 100

A: the discharge capacity of the 2nd working electrode in initial 0.1C charge and discharge cycles

B: the discharge capacity of the 2nd working electrode in the charge and discharge cycles of last 0.1C

Show the result in table 29.It should be noted that description here is will to regard cathode as to electrode, working electrode is regarded as just Pole.

Table 29

	EB9	EB10	EB11	EB12	CB6
						Capacity maintenance rate (%)	98.1	98.7	98.9	99.8	98.8

Any non-aqueous electrolyte secondary battery has carried out discharge and recharge reaction well, it is shown that capacity appropriate maintains Rate.The capacity maintenance rate of especially EB10, EB11, EB12 are very excellent.

(evaluation example 28: the invertibity of charge and discharge)

3 following charge and discharge cycles are carried out to EB9~EB12, CB6 with charge-discharge magnification 0.1C, that is, in 25 DEG C of progress CC Charging (constant current charging) is until voltage reaches 2.0V, then carries out CC electric discharge (constant current electric discharge) until voltage reaches The charge and discharge cycles of the 2.0V-0.01V of 0.01V.The charging and discharging curve of each non-aqueous electrolyte secondary battery is shown in Figure 81~figure 85。

As shown in Figure 81~Figure 85, it is known that EB9~EB12 is in the same manner as the CB6 for having used general electrolyte, reversibly Carry out discharge and recharge reaction.

(EB13)

Using electrolyte E9, in addition to this, non-aqueous electrolyte secondary battery EB13 is got similarly with EB9.

(evaluation example 29: the multiplying power property under low temperature)

Using EB13 and CB6, the multiplying power property of following -20 DEG C of evaluation.Show the result in Figure 86 and Figure 87.

(1) electric current is flowed towards progress lithium to the direction that cathode (evaluation electrode) occludes.

(2) voltage range: 2V → 0.01V (v.s.Li/Li+)

(3) multiplying power: 0.02C, 0.05C, 0.1C, 0.2C, 0.5C (electric current stops after reaching 0.01V)

It should be noted that 1C indicates current value needed for being kept battery fully charged in 1 hour at a certain current or electric discharge.

The voltage curve of EB13 under each current ratio known to Figure 86 and Figure 87 is shown compared with the voltage curve of CB6 High voltage is shown.Even if the result demonstrate non-aqueous electrolyte secondary battery of the invention also show at low ambient temperatures it is excellent Multiplying power property.

(embodiment 2-1)

Polyacrylic acid (PAA) is dissolved in pure water, prepares binder solution.Mixing flakey is added to the binder solution Powdered graphite prepares the negative electrode material together of pulp-like.The ratio of components of each ingredient (solid component) in slurry is graphite: PAA=90: 10 (mass ratioes).

The slurry is coated on to the surface of 18 μm of thickness of electrolytic copper foil (collector) using scraper, is formed on copper foil negative Pole active material layer.

Thereafter, 20 minutes dry at 80 DEG C, it evaporates pure water from negative electrode active material layer and removes.After drying, roll-in is utilized Machine makes collector and negative electrode active material layer closely sealed engagement securely.It is dried in vacuo 6 hours at 80 DEG C, it is living to obtain cathode Property material layer with a thickness of 30 μm or so of cathode.

Use the cathode of above-mentioned production as evaluation electrode, makes non-aqueous electrolyte secondary battery (half-cell).To electrode For metallic lithium foil (500 μm of thickness).

φ 15mm will be cut into electrode, will evaluation electrode be cut into φ 11mm, by separator (400 μm of thickness Whatman glass fiber filter paper) it is clipped between the two and electrode body battery is made.By the electrode body battery container in battery case In (precious Izumi Ltd. CR2032 button cell).It is then injected into electrolyte E8, it is battery case is closed and obtain embodiment 2-1 Non-aqueous electrolyte secondary battery.By the non-water power of the non-aqueous electrolyte secondary battery of embodiment 2-1 and each embodiment below The detailed content of solution electrolitc secondary cell is shown in the table 40 at the end on embodiment column.

(embodiment 2-2)

Use CMC and SBR mixture (CMC:SBR=1:1 by quality ratio) replace PAA as binder, and press with Mass ratio meter active material: binder=98:2 mode uses, and in addition to this, makes cathode in the same manner as embodiment 2-1, The remaining non-aqueous electrolyte secondary battery that embodiment 2-2 is got similarly with embodiment 2-1.

(comparative example 2-1)

Use and replace PAA as binder with the PVdF of PAA same amount, in addition to this, is made in the same manner as embodiment 2-1 negative Pole, remaining gets similarly the non-aqueous electrolyte secondary battery of comparative example 2-1 with embodiment 2-1.

(comparative example 2-2)

Use and replace PAA as binder with the PVdF of PAA same amount, in addition to this, is made in the same manner as embodiment 2-1 negative Pole.Use the cathode as evaluation electrode, and replaces electrolyte E8 using electrolyte C5, it is in addition to this, same as embodiment 2-1 Ground obtains non-aqueous electrolyte secondary battery.

Using the non-aqueous electrolyte secondary battery of embodiment 2-1 and 2-2 and comparative example 2-1 and 2-2, multiplying power is evaluated respectively Capacity characteristic, cycle capacity maintenance rate, part throttle characteristics.

(evaluation example 30: rate capability)

(1) electric current is flowed towards the direction that lithium is occluded to cathode is carried out.

(2) voltage range: 2V → 0.01V (v.s.Li/Li⁺)

(3) multiplying power: 0.1C, 0.2C, 0.5C, 1C, 2C, 5C, 10C, 0.1C (electric current stops after reaching 0.01V)

(4) each multiplying power respectively carries out 3 (total 24 circulations) measurements

The current capacity under the current capacity and each C multiplying power of 0.1C is measured under the conditions described above, finds out the electricity of 2C multiplying power Current capacity relative to the current capacity of 0.1C ratio and 5C multiplying power current capacity relative to 0.1C current capacity ratio.It will knot Fruit is shown in table 30.It should be noted that 1C indicates electric current needed for being kept battery fully charged in 1 hour at a certain current or electric discharge Value.

(evaluation example 31: cycle capacity maintenance rate)

As cycle capacity maintenance rate, the current capacity that the current capacity of the 25th circulation is recycled relative to the 1st time is calculated Ratio.Show the result in table 30.

Table 30

By the comparison of embodiment 2-1 and comparative example 2-1 it is found that electrolyte and PAA binder of the invention combines and this hair Bright electrolyte is compared with the combination of PVdF binder, the part throttle characteristics of cycle capacity maintenance rate and high magnification side (5C/0.1C) It substantially increases.It should be noted that the cycle capacity maintenance rate due to comparative example 2-2 is high, it is believed that the circulation in comparative example 2-1 The reduction phenomenon of capacity maintenance rate is electrolyte of the invention and phenomenon peculiar in the combination of PVdF binder.

In addition by the comparison of embodiment 2-2 and comparative example 2-1 it is found that electrolyte and CMC-SBR binder of the invention Combination, compared with the combination of electrolyte of the invention and PVdF binder and cycle capacity maintenance rate and high magnification side (5C/ Part throttle characteristics 0.1C) substantially increases.

It should be noted that cycle capacity maintenance rate is high although having used PVdF binder in comparative example 2-2, therefore, it is considered that making When with electrolyte of the invention, need appropriately combined with binder.

The first charging and discharging curve of the non-aqueous electrolyte secondary battery of embodiment 2-1,2-2 and comparative example 2-1 is shown in Figure 88.

According to Figure 88, it is thus identified that nearby side reaction is produced in primary charging 1.3V (to Li) in comparative example 2-1, with this Relatively, since the appropriately combined of electrolyte and binder of the invention inhibits side reaction in embodiment 2-1,2-2.As a result, Speculate that cycle characteristics improves in embodiment 2-1,2-2.The reasons why inhibiting side reaction is still uncertain, but may be with hydrophilic group Caused by the protective effect that the binder of group generates.

In addition, the charging and discharging curve of the high magnification side (5C) of embodiment 2-1 and comparative example 2-1 is compared, as a result implementing The plateau region from cell reaction is had found in example 2-1, it is in contrast, anti-from battery without discovery in comparative example 2-1 The plateau region answered, only the principle by absorption system has obtained micro charging capacity.Thus, thus it is speculated that load is special in embodiment 2-1 Property improve not only due to adsorption capacity increases, and reduces concentration overvoltage by the lithium supply of PAA binder effect As a result.

(embodiment 2-3)

The mixture (CMC:SBR=1:1 by quality ratio) of CMC and SBR is dissolved in pure water, prepares binder solution. Admixed graphite powder is added to the binder solution, prepares the cathode agent of pulp-like.Each ingredient (solid component) in slurry Ratio of components be graphite: CMC:SBR=98:1:1 (mass ratio).

Using 20 μm of thickness of electrolytic copper foil as cathode collector, applied using scraper on the surface of the cathode collector The above-mentioned slurry of cloth, forms negative electrode active material layer on the current collector.

Thereafter, 20 minutes dry at 80 DEG C, so that organic solvent is volatilized from negative electrode active material layer and removes.After drying, utilize Roll squeezer makes cathode collector and negative electrode active material layer closely sealed engagement securely.It is dried in vacuo 6 hours at 100 DEG C, The weight per unit area for forming negative electrode active material layer is 8.5mg/cm²The cathode of left and right.

Positive electrode active material layer has positive active material, binder and conductive auxiliary agent.Use NCM523 living as anode Property substance, uses PVDF to use AB as conductive auxiliary agent as binder.Positive collector is by 20 μm of thickness of aluminium foil structure At.Positive active material when positive electrode active material layer to be set as to 100 mass parts and binder and conductive auxiliary agent contain quality Than for 94:3:3.

NCM523, PVDF and AB are mixed in a manner of becoming above-mentioned mass ratio, adds and is pasted as the NMP of solvent The anode mixture of shape.The anode mixture of the paste is coated on to the surface of positive collector using scraper, forms positive-active Material layer.By the way that positive electrode active material layer is 20 minutes dry at 80 DEG C, to remove NMP by volatilization.It will using roll squeezer The compound of positive electrode active material layer and positive collector compresses, and makes anode collector and positive electrode active material layer securely Closely sealed engagement.Obtained binding element is heated 6 hours at 120 DEG C with vacuum drier, defined shape is cut into, obtains anode.

Using above-mentioned anode, cathode and electrolyte E8, a kind of lamination as non-aqueous electrolyte secondary battery is made Type lithium ion secondary battery.Specifically, cellulosic nonwoven fabric (thickness 20 of the sandwiched as separator between a positive electrode and a negative electrode μm) and polar plate group is made.Two one group of laminated film of the polar plate group is covered, after three sides are sealed, to what is taken the shape of a bag Laminated film injects above-mentioned electrolyte.Thereafter, it is sealed remaining on one side, thus obtains four sides and be hermetically sealed, be closed The non-aqueous electrolyte secondary battery of the embodiment 2-3 of polar plate group and electrolyte.

(comparative example 2-3)

Use the PVdF of 10 mass % to replace CMC-SBR as binder, in addition to this, is made in the same manner as embodiment 2-3 Make cathode, remaining gets similarly the non-aqueous electrolyte secondary battery of comparative example 2-3 with embodiment 2-3.

(comparative example 2-4)

Electrolyte E8 is replaced in addition to this to get similarly the non-of comparative example 2-4 with embodiment 2-3 using electrolyte C5 Water-Electrolyte secondary cell.

(comparative example 2-5)

90 mass parts of natural graphite as negative electrode active material and the PVdF10 mass parts as binder are mixed.Make The mixture is scattered in suitable ion exchange water, obtains the cathode agent of pulp-like.Prepare 20 μm of thickness of copper foil as negative Pole collector.Using scraper, above-mentioned cathode agent is coated on the surface of cathode collector membranaceous.By cathode agent It is dry with the compound of cathode collector and remove water, it followed by pressurizes, obtains binding element.By obtained binding element with very Empty drying machine 120 DEG C heat drying 6 hours, obtain in the cathode cathode for being formed with negative electrode active material layer on collector.

The anode of anode and the non-aqueous electrolyte secondary battery of embodiment 2-3 is carried out similarly manufacture.Except using this just Other than pole, cathode and electrolyte C5, the non-aqueous electrolyte secondary battery of comparative example 2-5 is got similarly with embodiment 2-3.

(evaluation example 32: input-output characteristic)

It is defeated by condition evaluating below using the non-aqueous electrolyte secondary battery of embodiment 2-3 and comparative example 2-3~2-5 Enter (charging) characteristic.

(1) voltage range: 3V-4.2V is used

(2) capacity: 13.5mAh

(3) SOC80%

(4) temperature: 0 DEG C, 25 DEG C

(5) measurement number: each 3 times

Evaluation condition be 80%, 0 DEG C of charged state (SOC), 25 DEG C, using voltage range 3V-4.2V, capacity 13.5mAh. SOC80%, 0 DEG C of e.g. input characteristics as in the case where refrigerating chamber etc. uses are not easy the region embodied.Embodiment 2-3 and The evaluation of the input characteristics of comparative example 2-3,2-4 is to carry out input in 3 times 2 seconds and input in 5 seconds respectively.By the evaluation knot of input characteristics Fruit is shown in table 31, table 32." inputting within 2 seconds " in table indicates the input after charging starts 2 seconds, and " inputting within 5 seconds " indicates charging Input after starting 5 seconds.It should be noted that in table 31,32, referred to as by electrolyte E8 used in embodiment 2-3 and comparative example 2-3 For " FSA ", electrolyte C5 used in comparative example 2-4 and comparative example 2-5 is referred to as " ECPF ".

Table 31

(25 DEG C of SOC80%)

Table 32

(0 DEG C of SOC80%)

0 DEG C and 25 DEG C the two at a temperature of, embodiment 2-3 compared with comparative example 2-3~2-5, input (charging) characteristic It improves.This is and has used effect caused by binder (CMC-SBR) and electrolyte of the invention with hydrophilic radical, especially Even if being to also show high input (charging) characteristic at 0 DEG C, even if therefore showing the lithium ion in electrolyte at low temperature Movement also can successfully carry out.

(embodiment 2-4)

Use CMC and SBR mixture (CMC:SBR=1:1 by quality ratio) replace PAA as binder, and press with Mass ratio meter active material: binder=98:2 mode uses, and makes 100 DEG C of vacuum drying temperature, in addition to this, with reality Applying a 2-1 and being identically formed the weight per unit area of negative electrode active material layer is 4mg/cm²The cathode of left and right.

As a positive electrode active material using NCM523, use PVDF as binder, use AB as conductive auxiliary agent.As Positive collector uses 20 μm of aluminium foil of thickness.Positive electrode active material layer is set as to positive active material when 100 mass parts The mass ratio that contains with conductive auxiliary agent and binder is 90:8:2.Using these positive active materials, conductive auxiliary agent, binder and Positive collector gets similarly anode with embodiment 2-3.

Using above-mentioned anode, cathode and above-mentioned electrolyte E11, get similarly embodiment 2-4's with embodiment 2-3 Non-aqueous electrolyte secondary battery.

(comparative example 2-6)

Electrolyte E11 is replaced in addition to this to get similarly the non-of comparative example 2-6 with embodiment 2-4 using electrolyte C5 Water-Electrolyte secondary cell.

(evaluation example 33: the cyclic durability of battery)

Using the non-aqueous electrolyte secondary battery of embodiment 2-4 and comparative example 2-6,500 iterative cycles examinations are respectively carried out It tests, that is, charge to 4.1V under conditions of the CC of 25 DEG C of temperature, 1C charging, after stopping 1 minute, discharged, be discharged to the CC of 1C 3.0V, the circulation stopped 1 minute.The result for measuring the discharge capacity sustainment rate of the 500th circulation is shown in table 33.Discharge capacity Sustainment rate is that the percentage of value obtained by the discharge capacity as being recycled with the 500th time is held divided by first electric discharge { (follows for the 500th time The discharge capacity of ring)/(first discharge capacity) × 100 } value that finds out.

In addition, being adjusted by the CCCV with 25 DEG C of temperature, 0.5C to voltage 3.5V, being carried out with 3C in the 200th circulation 10 seconds CC electric discharge when voltage variety (discharge before voltage and electric discharge 10 seconds after voltage difference) and current value using ohm determine Rule measurement D.C. resistance.Show the result in table 33.

Table 33

E11:3.9M LiFSA/DMC, C5:1.0M LiPF₆/EC+DEC

As shown in embodiment 2-4, related to by combining the binder being made of the polymer with hydrophilic radical with the present invention And electrolyte of the present invention, can be made cycle life improve and low-resistance secondary cell.

(embodiment 2-5)

By active material by quality ratio: CMC-SBR is replaced using PAA in the way of binder=90:10, in addition to this, Cathode is made in the same manner as embodiment 2-4, using the cathode, in addition to this, gets similarly embodiment 2-5 with embodiment 2-4 Non-aqueous electrolyte secondary battery.

(evaluation example 34: the high-temperature storage patience of battery)

Using the lithium secondary battery of embodiment 2-4,2-5, comparative example 2-6, store at 60 DEG C high-temperature storage examination in 1 week It tests.Before high-temperature storage on-test, on the basis of charging capacity when charging to 4.1V from 3.0V by CC-CV (SOC100), after relative to benchmark CC 20% (being adjusted to SOC80) of electric discharge, start high-temperature storage test.It is tested in high-temperature storage Afterwards with 1C CC-CV to 3.0V, according at this time discharge capacity and storage before the ratio between SOC80 capacity, reservation is calculated as follows and holds Amount.Show the result in table 34.

Retention capacity=100 × (the CC-CV discharge capacity after storage)/(the SOC80 capacity before storage)

Table 34

E11:3.9M LiFSA/DMC, C5:1.0M LiPF₆/EC+DEC

As shown in embodiment 2-4,2-5, by combining the binder and this hair that are made of the polymer with hydrophilic radical The bright electrolyte of the present invention being related to, the capacity after high-temperature storage improve.

(evaluation example 35: the cyclic durability of battery)

In room temperature, the range of 3.0V~4.1V (vs.Li benchmark) to each non-aqueous solution electrolysis of embodiment 2-4 and comparative example 2-6 500 circulation CC charge and discharge are repeated in electrolitc secondary cell, measure capacity discharge current (Ah) and the charging current in each circulation Capacity (Ah).Then, the coulombic efficiency (%) in each circulation is calculated based on measured value, further calculated from when first charge and discharge The average value of coulombic efficiency when circulation (that is 1 time) is to 500 circulations.In addition, putting when measuring first charge and discharge Discharge capacity when capacitance and 500 circulations.The capacity of each non-aqueous electrolyte secondary battery when then, by first charge and discharge It is set as 100%, calculates the capacity maintenance rate (%) of each non-aqueous electrolyte secondary battery when recycling 500 times.Coulombic efficiency according to { (capacity discharge current)/(charging current capacity) } × 100 calculate.Show the result in table 35.

Table 35

E11:3.9M LiFSA/DMC, C5:1.0M LiPF₆/(EC/DEC)

As shown in table 35, the secondary electricity of nonaqueous electrolyte of the non-aqueous electrolyte secondary battery of embodiment 2-4 and comparative example 2-6 Pond is compared, and coulombic efficiency is high, and capacity maintenance rate is also high.That is, combination is as the LiFSA of metal salt and as binder The case where CMC-SBR with combine the LiPF as metal salt₆It compares, can improve non-with the case where CMC-SBR as binder The cycle characteristics of Water-Electrolyte secondary cell.More specifically, use the polymer with hydrophilic radical as the sheet of binder In the non-aqueous electrolyte secondary battery of invention, metal salt of the LiFSA as electrolyte is preferably used.

It should be noted that if side reaction (that is reaction other than the cell reactions such as decomposition of electrolyte) in cathode Reducing then coulombic efficiency has raised trend.Side reaction in cathode is that the irreversible of Li is irreversibly captured in cathode mostly Reaction can become the reason of battery capacity reduces.Thus it is speculated that inhibiting in each non-aqueous electrolyte secondary battery of embodiment 4 Above-mentioned side reaction, as a result, capacity maintenance rate when 500 circulations improves.

It is only limitted to refer to, coulombic efficiency shown in table 35 is the average value of 500 circulations, that is to say, that is recycled every time Value.Therefore, if 500 cycle values are accumulated, the difference of the coulombic efficiency of embodiment 2-4 and comparative example 2-6 is very big.

(embodiment 2-6)

It is (NCM523:AB:PVdF=90:8:2) and identical with embodiment 2-1 using anode identical with embodiment 2-4 Cathode (natural graphite: PAA=90:10) in addition to this gets similarly the nonaqueous electrolyte of embodiment 2-6 with embodiment 2-3 Secondary cell.

(embodiment 2-7)

It is (NCM523:AB:PVdF=90:8:2) and identical with embodiment 2-2 using anode identical with embodiment 2-4 Cathode (natural graphite: CMC:SBR=98:1:1) in addition to this gets similarly the non-aqueous of embodiment 2-7 with embodiment 2-3 Electrolyte secondary battery.

(comparative example 2-7)

Using electrolyte C5, in addition to this, the non-aqueous solution electrolysis of comparative example 2-7 is obtained with method same as embodiment 2-6 Electrolitc secondary cell.

(comparative example 2-8)

Using electrolyte C5, in addition to this, the non-aqueous solution electrolysis of comparative example 2-8 is obtained with method same as embodiment 2-7 Electrolitc secondary cell.

(evaluation example 36: the cyclic durability of battery)

With method same as above-mentioned " evaluation example 33: the cyclic durability of battery " to each non-of embodiment 2-6,2-7 200 cycle charge-discharges are repeated in Water-Electrolyte secondary cell, calculate each non-aqueous electrolyte secondary battery when 200 circulations Capacity maintenance rate (%) and coulombic efficiency (%, 200 times circulation average values).Show the result in table 36.

Table 36

E8:4.5M LiFSA/AN

As shown in table 36, the secondary electricity of nonaqueous electrolyte of the non-aqueous electrolyte secondary battery of embodiment 2-6 and embodiment 2-7 Pond is compared, and capacity maintenance rate and coulombic efficiency are excellent.According to the result, it may be said that as binder, more preferably PAA.

(evaluation example 37: the cyclic durability of battery)

Substantially samely with above-mentioned " evaluation example 36: the cyclic durability of battery ", to embodiment 2-6,2-7 and comparative example The capacity of each non-aqueous electrolyte secondary battery when each non-aqueous electrolyte secondary battery of 2-7,2-8 calculate 203 circulations maintains Rate (%).More specifically, in this experiment, initial for test with the 3rd circulation, it finds out from this circulation and carries out again 200 times Capacity maintenance rate when cycle charge-discharge.In addition, initial in test, that is, when 3 circulations, by with 25 DEG C of temperature, 0.5C CCCV be adjusted to voltage 3.5V after, with the CC electric discharge of 3C progress 10 seconds when voltage variety (voltage and electric discharge 10 seconds before discharging The difference of voltage afterwards) and current value using Ohm's law measure D.C. resistance.Then, using D.C. resistance at this time as initial DC Resistance.Show the result in table 37.

Table 37

E8:4.5M LiFSA/AN, C5:1.0M LiPF₆/(EC/DEC)

As shown in table 37, in each nonaqueous electrolyte two of embodiment 2-6, embodiment 2-7, comparative example 2-7 and comparative example 2-8 In primary cell, 203 times circulation when capacity maintenance rate it is roughly the same, be high level.Embodiment 2-6 and 2-7 are compared, it can To say as binder, PAA is excellent, is compared to comparative example 2-7 and 2-8, it may be said that as binder, CMC-SBR is excellent. That is, in the non-aqueous electrolyte secondary battery of the invention for having used electrolyte of the present invention, as binder, it may be said that Compared with using CMC-SBR, PAA is more preferably used.

It should be noted that using LiFSA as the secondary electricity of nonaqueous electrolyte of the embodiment 2-6 and embodiment 2-7 of metal salt Pond with use LiPF₆Comparative example 2-6 as metal salt is compared with the non-aqueous electrolyte secondary battery of comparative example 2-7, initial straight Leakage resistance is low.Therefore, in order to have both capacity maintenance rate raising and resistance increase inhibition, it may be said that use electrolysis of the invention Liquid and use the binder with hydrophilic radical secondary as the nonaqueous electrolyte of the embodiment 2-6 and embodiment 2-7 of binder Battery, non-aqueous electrolyte secondary battery i.e. of the invention are advantageous.

(evaluation example 38: the high-temperature storage patience of battery)

Using the non-aqueous electrolyte secondary battery of embodiment 2-6,2-7, comparative example 2-7,2-8, store 1 week at 60 DEG C High-temperature storage test.Before high-temperature storage on-test, charging capacity when being charged to 4.1V from 3.0V by CC-CV is Benchmark is set as SOC100.Then, after being adjusted to SOC80 relative to benchmark CC electric discharge 20%, start high-temperature storage test.? After high-temperature storage test, CC-CV to 3.0V is carried out with 1C, based at this time discharge capacity and storage before the ratio between SOC80 capacity, It is calculate by the following formula residual capacity.

Calculate retention capacity.Show the result in table 38.

Table 38

E8:4.5M LiFSA/AN, C5:1.0M LiPF₆/(EC/DEC)

As shown in table 38, the secondary electricity of nonaqueous electrolyte of the non-aqueous electrolyte secondary battery of embodiment 2-6 and embodiment 2-7 Pond is compared, and residual capacity is big.That is, combination LiFSA/AN and PAA embodiment 2-6 non-aqueous electrolyte secondary battery with Combination LiFSA/AN is compared with the non-aqueous electrolyte secondary battery of the embodiment 2-7 of CMC-SBR, high-temperature storage excellent.Separately Outside, according to this as a result, combining the sheet of electrolyte and the binder being made of the polymer with hydrophilic radical of the invention The non-aqueous electrolyte secondary battery of invention with combine common electrolyte and be made of the polymer with hydrophilic radical High-temperature storage patience more than the existing non-aqueous electrolyte secondary battery of binder is same or same.

(other mode II)

As electrolyte of the invention, electrolyte below is specifically enumerated.It should be noted that electrolyte below also includes Electrolyte through describing.

(electrolyte A)

Electrolyte of the invention is manufactured as follows.

1,2- dimethoxy-ethane about 5mL as organic solvent is put into the flask for having stirrer and thermometer. Under agitation, by solution temperature be maintained at 40 DEG C it is below in a manner of 1,2- dimethoxy-ethane into above-mentioned flask it is slow Add (the CF as lithium salts in ground₃SO₂)₂NLi makes it dissolve.Due in (the CF that about 13g is added₃SO₂)₂At the time of NLi (CF₃SO₂)₂Solution temperature in flask is heated up to 50 so above-mentioned flask is put into thermostat by the dissolution lull of NLi DEG C, make (CF₃SO₂)₂NLi dissolution.Due in (the CF that about 15g is added₃SO₂)₂(CF at the time of NLi₃SO₂)₂The dissolution of NLi is again It stagnates, so 1 drop 1,2- dimethoxy-ethane, later (CF is added dropwise with dropper₃SO₂)₂NLi dissolution.Further slowly add (CF₃SO₂)₂Whole defined (CF is added in NLi₃SO₂)₂NLi.Obtained electrolyte is moved into 20mL volumetric flask, is added 1,2- Dimethoxy-ethane is until volume becomes 20mL.The volume of obtained electrolyte is 20mL, (CF contained by the electrolyte₃SO₂)₂NLi is 18.38g.As electrolyte A.(CF in electrolyte A₃SO₂)₂The concentration of NLi is 3.2mol/L, and density is 1.39g/cm³.Density is measured at 20 DEG C.

(electrolyte B)

With method same as electrolyte A, (CF is manufactured₃SO₂)₂The concentration of NLi is 2.8mol/L, density 1.36g/cm³ Electrolyte B.

(electrolyte C)

It will be put into the flask for having stirrer as the acetonitrile of organic solvent about 5mL.Under agitation, to above-mentioned burning Acetonitrile in bottle slowly adds the (CF as lithium salts₃SO₂)₂NLi makes it dissolve.(CF as defined in addition₃SO₂)₂After NLi, stir Mix an evening.Obtained electrolyte is moved into 20mL volumetric flask, acetonitrile is added until volume becomes 20mL.As electrolyte C. It should be noted that above-mentioned manufacture is carried out in the glove box under non-reactive gas ambient.

(CF in electrolyte C₃SO₂)₂The concentration of NLi is 4.2mol/L, density 1.52g/cm³。

(electrolyte D)

With method same as electrolyte C, (CF is manufactured₃SO₂)₂The concentration of NLi is 3.0mol/L, density 1.31g/cm³ Electrolyte D.

(electrolyte E)

Use sulfolane as organic solvent, in addition to this, with method same as electrolyte C, manufactures (CF₃SO₂)₂NLi Concentration be 3.0mol/L, density 1.57g/cm³Electrolyte E.

(electrolyte F)

Use dimethyl sulfoxide as organic solvent, in addition to this, with method same as electrolyte C, manufacture (CF₃SO₂)₂The concentration of NLi is 3.2mol/L, density 1.49g/cm³Electrolyte F.

(electrolyte G)

Use (FSO₂)₂NLi is as lithium salts, using 1,2- dimethoxy-ethane as organic solvent, in addition to this, with The same method of electrolyte C manufactures (FSO₂)₂The concentration of NLi is 4.0mol/L, density 1.33g/cm³Electrolyte G.

(electrolyte H)

With method same as electrolyte G, (FSO is manufactured₂)₂The concentration of NLi is 3.6mol/L, density 1.29g/cm³'s Electrolyte H.

(electrolyte I)

With method same as electrolyte G, (FSO is manufactured₂)₂The concentration of NLi is 2.4mol/L, density 1.18g/cm³'s Electrolyte I.

(electrolyte J)

Use acetonitrile as organic solvent, in addition to this, with method same as electrolyte G, manufactures (FSO₂)₂NLi's is dense Degree is 5.0mol/L, density 1.40g/cm³Electrolyte J.

(electrolyte K)

With method same as electrolyte J, (FSO is manufactured₂)₂The concentration of NLi is 4.5mol/L, density 1.34g/cm³'s Electrolyte K.

(electrolyte L)

It will be put into the flask for having stirrer as the dimethyl carbonate of organic solvent about 5mL.Under agitation, to Dimethyl carbonate in above-mentioned flask slowly adds the (FSO as lithium salts₂)₂NLi makes it dissolve.Addition total amount is 14.64g (FSO₂)₂After NLi, one evening of stirring.Obtained electrolyte is moved into 20mL volumetric flask, dimethyl carbonate is added until volume becomes At 20mL.As electrolyte L.It should be noted that above-mentioned manufacture is carried out in the glove box under non-reactive gas ambient.

(FSO in electrolyte L₂)₂The concentration of NLi is 3.9mol/L, and the density of electrolyte L is 1.44g/cm³。

(electrolyte M)

With method same as electrolyte L, (FSO is manufactured₂)₂The concentration of NLi is 2.9mol/L, density 1.36g/cm³'s Electrolyte M.

(electrolyte N)

It will be put into the flask for having stirrer as the methyl ethyl carbonate of organic solvent about 5mL.Under agitation, to Methyl ethyl carbonate in above-mentioned flask slowly adds the (FSO as lithium salts₂)₂NLi makes it dissolve.Addition total amount is 12.81g (FSO₂)₂After NLi, one evening of stirring.Obtained electrolyte is moved into 20mL volumetric flask, methyl ethyl carbonate is added until volume becomes At 20mL.As electrolyte N.It should be noted that above-mentioned manufacture is carried out in the glove box under non-reactive gas ambient.

(FSO in electrolyte N₂)₂The concentration of NLi is 3.4mol/L, and the density of electrolyte N is 1.35g/cm³。

(electrolyte O)

It will be put into the flask for having stirrer as the diethyl carbonate of organic solvent about 5mL.Under agitation, to Diethyl carbonate in above-mentioned flask slowly adds the (FSO as lithium salts₂)₂NLi makes it dissolve.Addition total amount is 11.37g (FSO₂)₂After NLi, one evening of stirring.Obtained electrolyte is moved into 20mL volumetric flask, diethyl carbonate is added until volume becomes At 20mL.As electrolyte O.It should be noted that above-mentioned manufacture is carried out in the glove box under non-reactive gas ambient.

(FSO in electrolyte O₂)₂The concentration of NLi is 3.0mol/L, and the density of electrolyte O is 1.29g/cm³。

The list of above-mentioned electrolyte is shown in table 39.

Table 39

LiTFSA:(CF₃SO₂)₂NLi, LiFSA:(FSO₂)₂NLi, AN: acetonitrile, DME:1,2- dimethoxy-ethane, DMSO: Dimethyl sulfoxide, SL: sulfolane, DMC: dimethyl carbonate, EMC: methyl ethyl carbonate, DEC: diethyl carbonate

Table 40

Claims

1. a kind of non-aqueous electrolyte secondary battery, containing cathode, electrolyte and anode,

For the peak intensity from organic solvent in the vibrational spectrum of the electrolyte, by the original peak of the organic solvent When intensity is set as Io, the intensity at the peak after the peak shift is set as Is, meet Is > Io；

Further satisfaction following condition 1 and/or condition 2,

Condition 1:

The electrolyte contains salt and the organic solvent with miscellaneous element, the salt with alkali or alkaline earth metal be cation and Contain element sulphur and oxygen element in the chemical structure of anion,

Salt in the electrolyte only by being constituted alkali or alkaline earth metal as the salt of cation,

Organic solvent in the electrolyte be selected from nitrile, amides, esters, ketone, acid anhydrides, sulfone class, sulfoxide type, nitro class, Heterocyclic,

The envelope containing S, O with S=O structure is formd on the surface of the cathode and/or the anode,

Condition 2:

The electrolyte contains with salt that alkali or alkaline earth metal is cation and organic solvent with miscellaneous element,

The cathode includes binder, which is made of the polymer with hydrophilic radical.

2. non-aqueous electrolyte secondary battery according to claim 1, wherein the esters are carbonates, isocyanates Class, cyclic annular esters or phosphoric acid ester.

3. non-aqueous electrolyte secondary battery according to claim 1, wherein the heterocyclic be epoxies,Azole, furan It mutters class, cyclic annular esters, heteroaromatic class or ethers, wherein the ethers is selected from tetrahydrofuran, 1,2- bis-Alkane, 1,3- bis-Alkane, 1,4- bis-Alkane, 2,2- dimethyl -1,3- dioxolanes, 2- methyl oxinane, 2- methyltetrahydrofuran, crown ether.

4. non-aqueous electrolyte secondary battery according to claim 1, wherein the organic solvent in the electrolyte is selected from second Nitrile, propionitrile, acrylonitrile, malononitrile, tetrahydrofuran, 1,2- bis-Alkane, 1,3- bis-Alkane, 1,4- bis-Alkane, 2,2- dimethyl- 1,3- dioxolanes, 2- methyl oxinane, 2- methyltetrahydrofuran, crown ether, ethylene carbonate, propylene carbonate, formamide, N,N-dimethylformamide, DMAC N,N' dimethyl acetamide, N-Methyl pyrrolidone, isopropyl isocyanate, n-propyl isocyanic acid Ester, chloromethane based isocyanate, methyl acetate, ethyl acetate, propyl acetate, methyl propionate, methyl formate, Ethyl formate, acetic acid Vinyl acetate, methyl acrylate, methyl methacrylate, Glycidyl methyl ether, epoxy butane, 2- ethyl ethylene oxide, Azoles, 2- ethylAzoles,Oxazoline, 2- methyl -2-Oxazoline, acetone, methyl ethyl ketone, methyl iso-butyl ketone (MIBK), acetic anhydride, propionic acid Acid anhydride, dimethyl sulfone, sulfolane, dimethyl sulfoxide, 1- nitropropane, 2- nitropropane, furans, furfural, gamma-butyrolacton, γ-penta Lactone, δ-valerolactone, thiophene, pyridine, tetrahydro-pyrokomane, 1- crassitude, N-methylmorpholine, trimethyl phosphate, phosphoric acid The linear carbonate that triethyl or the following general formula (10) indicate,

R¹⁹OCOOR²⁰General formula (10)

R¹⁹、R²⁰It is each independently selected from the C for chain-like alkyl_nH_aF_bCl_cBr_dI_eOr contain cyclic alkyl in chemical structure C_mH_fF_gCl_hBr_iI_jAny one of, the integer that n is 1~6, the integer that m is 3~8, a, b, c, d, e, f, g, h, i, j are respectively only On the spot it is 0 or more integer, meets 2n+1=a+b+c+d+e, 2m-1=f+g+h+i+j.

5. non-aqueous electrolyte secondary battery according to claim 4, wherein the linear carbonate that the general formula (10) indicates It is dimethyl carbonate, diethyl carbonate or methyl ethyl carbonate.

6. non-aqueous electrolyte secondary battery according to claim 1, wherein meet the condition 1, the cathode of the cathode Contain carbon in active material.

7. non-aqueous electrolyte secondary battery according to claim 1, wherein meet the condition 1,

The chemical structure of the anion of the salt by the following general formula (1), general formula (2) or general formula (3) indicate,

(R¹X¹)(R²X²) N general formula (1)

R¹Selected from hydrogen, halogen, the alkyl that can be substituted with a substituent, the naphthenic base that can be substituted with a substituent, base can be substituted Substituted unsaturated alkyl, the unsaturated ring alkyl that can be substituted with a substituent, the aromatic group that can be substituted with a substituent, The heterocycle that can be substituted with a substituent, the alkoxy that can be substituted with a substituent, the unsaturated alkane that can be substituted with a substituent Oxygroup, the thio alkoxy that can be substituted with a substituent, the unsaturated thio alkoxy that can be substituted with a substituent, CN, SCN, OCN,

R²Selected from hydrogen, halogen, the alkyl that can be substituted with a substituent, the naphthenic base that can be substituted with a substituent, base can be substituted Substituted unsaturated alkyl, the unsaturated ring alkyl that can be substituted with a substituent, the aromatic group that can be substituted with a substituent, The heterocycle that can be substituted with a substituent, the alkoxy that can be substituted with a substituent, the unsaturated alkane that can be substituted with a substituent Oxygroup, the thio alkoxy that can be substituted with a substituent, the unsaturated thio alkoxy that can be substituted with a substituent, CN, SCN, OCN,

In addition, R¹And R²It can be mutually bonded and form ring,

X¹Selected from SO₂, S=O,

X²Selected from SO₂, S=O；

R³X³Y general formula (2)

R³Selected from hydrogen, halogen, the alkyl that can be substituted with a substituent, the naphthenic base that can be substituted with a substituent, base can be substituted Substituted unsaturated alkyl, the unsaturated ring alkyl that can be substituted with a substituent, the aromatic group that can be substituted with a substituent, The heterocycle that can be substituted with a substituent, the alkoxy that can be substituted with a substituent, the unsaturated alkane that can be substituted with a substituent Oxygroup, the thio alkoxy that can be substituted with a substituent, the unsaturated thio alkoxy that can be substituted with a substituent, CN, SCN, OCN,

X³Selected from SO₂, S=O,

Y is selected from O, S；

(R⁴X⁴)(R⁵X⁵)(R⁶X⁶) C general formula (3)

R⁴Selected from hydrogen, halogen, the alkyl that can be substituted with a substituent, the naphthenic base that can be substituted with a substituent, base can be substituted Substituted unsaturated alkyl, the unsaturated ring alkyl that can be substituted with a substituent, the aromatic group that can be substituted with a substituent, The heterocycle that can be substituted with a substituent, the alkoxy that can be substituted with a substituent, the unsaturated alkane that can be substituted with a substituent Oxygroup, the thio alkoxy that can be substituted with a substituent, the unsaturated thio alkoxy that can be substituted with a substituent, CN, SCN, OCN,

R⁵Selected from hydrogen, halogen, the alkyl that can be substituted with a substituent, the naphthenic base that can be substituted with a substituent, base can be substituted Substituted unsaturated alkyl, the unsaturated ring alkyl that can be substituted with a substituent, the aromatic group that can be substituted with a substituent, The heterocycle that can be substituted with a substituent, the alkoxy that can be substituted with a substituent, the unsaturated alkane that can be substituted with a substituent Oxygroup, the thio alkoxy that can be substituted with a substituent, the unsaturated thio alkoxy that can be substituted with a substituent, CN, SCN, OCN,

R⁶Selected from hydrogen, halogen, the alkyl that can be substituted with a substituent, the naphthenic base that can be substituted with a substituent, base can be substituted Substituted unsaturated alkyl, the unsaturated ring alkyl that can be substituted with a substituent, the aromatic group that can be substituted with a substituent, The heterocycle that can be substituted with a substituent, the alkoxy that can be substituted with a substituent, the unsaturated alkane that can be substituted with a substituent Oxygroup, the thio alkoxy that can be substituted with a substituent, the unsaturated thio alkoxy that can be substituted with a substituent, CN, SCN, OCN,

In addition, R⁴、R⁵、R⁶In wantonly 2 or 3 can be bonded and form ring,

X⁴Selected from SO₂, S=O,

X⁵Selected from SO₂, S=O,

X⁶Selected from SO₂, S=O.

8. non-aqueous electrolyte secondary battery according to claim 1, wherein meet the condition 1,

The chemical structure of the anion of the salt by the following general formula (4), general formula (5) or general formula (6) indicate,

(R⁷X⁷)(R⁸X⁸) N general formula (4)

R⁷、R⁸It is each independently C_nH_aF_bCl_cBr_dI_e(CN)_f(SCN)_g(OCN)_h,

N, a, b, c, d, e, f, g, h are each independently 0 or more integer, meet 2n+1=a+b+c+d+e+f+g+h,

In addition, R⁷And R⁸It can be mutually bonded and form ring, at this point, meet 2n=a+b+c+d+e+f+g+h,

X⁷Selected from SO₂, S=O,

X⁸Selected from SO₂, S=O；

R⁹X⁹Y general formula (5)

R⁹For C_nH_aF_bCl_cBr_dI_e(CN)_f(SCN)_g(OCN)_h,

X⁹Selected from SO₂, S=O,

Y is selected from O, S；

(R¹⁰X¹⁰)(R¹¹X¹¹)(R¹²X¹²) C general formula (6)

R¹⁰、R¹¹、R¹²It is each independently C_nH_aF_bCl_cBr_dI_e(CN)_f(SCN)_g(OCN)_h,

R¹⁰、R¹¹、R¹²In wantonly 2 can be bonded and form ring, at this point, formed ring group meet 2n=a+b+c+d+e+f+g+ H, in addition, R¹⁰、R¹¹、R¹²This 3 can be bonded and form ring, at this point, 2 in 3 group meets 2n=a+b+c+d+e+f+ G+h, 1 group meet 2n-1=a+b+c+d+e+f+g+h,

X¹⁰Selected from SO₂, S=O,

X¹¹Selected from SO₂, S=O,

X¹²Selected from SO₂, S=O.

9. non-aqueous electrolyte secondary battery according to claim 1, wherein meet the condition 1, the anode have by The anode collector that aluminum or aluminum alloy is constituted.

10. non-aqueous electrolyte secondary battery according to claim 1, wherein meet the condition 1, the envelope containing S, O S concentration and O concentration change in charge and discharge.

11. non-aqueous electrolyte secondary battery according to claim 1, wherein meet the condition 1, the envelope containing S, O Thickness change in charge and discharge.

12. non-aqueous electrolyte secondary battery according to claim 1, wherein meet the condition 1, the envelope containing S, O S containing 2 atom % or more.

13. non-aqueous electrolyte secondary battery according to claim 1, wherein meet the condition 2, it is described with hydrophilic The polymer of group contains multiple carboxyls and/or sulfo group in a molecule.

14. non-aqueous electrolyte secondary battery according to claim 1, wherein meet the condition 2, it is described with hydrophilic The polymer of group is water-soluble polymer.

15. non-aqueous electrolyte secondary battery according to claim 1, wherein meet the condition 2, it is described with hydrophilic The polymer of group is water-soluble polymer, and the water-soluble polymer contains multiple carboxyls and/or sulfo group in a molecule.

16. non-aqueous electrolyte secondary battery according to claim 1, wherein meet the condition 2, in the electrolyte The chemical structure of the anion of the salt contains selected from least one of halogen, boron, nitrogen, oxygen, sulphur or carbon element.

17. non-aqueous electrolyte secondary battery according to claim 1, wherein meet the condition 2,

The chemical structure of the anion of salt described in the electrolyte by the following general formula (1), general formula (2) or general formula (3) indicate,

(R¹X¹)(R²X²) N general formula (1)

In addition, R¹And R²It can be mutually bonded and form ring,

X¹Selected from SO₂, C=O, C=S, R^aP=O, R^bP=S, S=O, Si=O,

X²Selected from SO₂, C=O, C=S, R^cP=O, R^dP=S, S=O, Si=O,

R^a、R^b、R^c、R^dIt is each independently selected from hydrogen, halogen, the alkyl that can be substituted with a substituent, can be substituted with a substituent Naphthenic base, the unsaturated ring alkyl that can be substituted with a substituent, can be substituted the unsaturated alkyl that can be substituted with a substituent The aromatic group of base substitution, the alkoxy that can be substituted with a substituent, can be taken the heterocycle that can be substituted with a substituent Unsaturated alkoxy, the thio alkoxy that can be substituted with a substituent, the unsaturation that can be substituted with a substituent replaced for base Thio alkoxy, OH, SH, CN, SCN, OCN,

In addition, R^a、R^b、R^c、R^dIt can be with R¹Or R²It is bonded and forms ring；

R³X³Y general formula (2)

X³Selected from SO₂, C=O, C=S, R^eP=O, R^fP=S, S=O, Si=O,

R^e、R^fIt is each independently selected from hydrogen, halogen, the alkyl that can be substituted with a substituent, the cycloalkanes that can be substituted with a substituent Base, the unsaturated ring alkyl that can be substituted with a substituent, can be substituted base and take the unsaturated alkyl that can be substituted with a substituent The aromatic group in generation, the alkoxy that can be substituted with a substituent, can be substituted base at the heterocycle that can be substituted with a substituent Substituted unsaturated alkoxy, the thio alkoxy that can be substituted with a substituent, the unsaturation that can be substituted with a substituent are thio Alkoxy, OH, SH, CN, SCN, OCN,

In addition, R^e、R^fIt can be with R³It is bonded and forms ring,

Y is selected from O, S；

(R⁴X⁴)(R⁵X⁵)(R⁶X⁶) C general formula (3)

In addition, R⁴、R⁵、R⁶In wantonly two or three can be bonded and form ring,

X⁴Selected from SO₂, C=O, C=S, R^gP=O, R^hP=S, S=O, Si=O,

X⁵Selected from SO₂, C=O, C=S, RⁱP=O, R^jP=S, S=O, Si=O,

X⁶Selected from SO₂, C=O, C=S, R^kP=O, R^lP=S, S=O, Si=O,

R^g、R^h、Rⁱ、R^j、R^k、R^lIt is each independently selected from hydrogen, halogen, the alkyl that can be substituted with a substituent, base can be substituted Substituted naphthenic base, the unsaturated alkyl that can be substituted with a substituent, the unsaturated ring alkyl that can be substituted with a substituent, can be with The aromatic group that is substituted with a substituent, the heterocycle that can be substituted with a substituent, the alkoxy that can be substituted with a substituent, can With the unsaturated alkoxy that is substituted with a substituent, the thio alkoxy that can be substituted with a substituent, can be substituted with a substituent Unsaturated thio alkoxy, OH, SH, CN, SCN, OCN,

In addition, R^g、R^h、Rⁱ、R^j、R^k、R^lIt can be with R⁴、R⁵Or R⁶It is bonded and forms ring.

18. non-aqueous electrolyte secondary battery according to claim 1, wherein meet the condition 2,

The chemical structure of the anion of salt described in the electrolyte by the following general formula (4), general formula (5) or general formula (6) indicate,

(R⁷X⁷)(R⁸X⁸) N general formula (4)

R⁷、R⁸It is each independently C_nH_aF_bCl_cBr_dI_e(CN)_f(SCN)_g(OCN)_h,

X⁷Selected from SO₂, C=O, C=S, R^mP=O, RⁿP=S, S=O, Si=O,

X⁸Selected from SO₂, C=O, C=S, R^oP=O, R^pP=S, S=O, Si=O,

R^m、Rⁿ、R^o、R^pIt is each independently selected from hydrogen, halogen, the alkyl that can be substituted with a substituent, can be substituted with a substituent Naphthenic base, the unsaturated ring alkyl that can be substituted with a substituent, can be substituted the unsaturated alkyl that can be substituted with a substituent The aromatic group of base substitution, the alkoxy that can be substituted with a substituent, can be taken the heterocycle that can be substituted with a substituent Unsaturated alkoxy, the thio alkoxy that can be substituted with a substituent, the unsaturation that can be substituted with a substituent replaced for base Thio alkoxy, OH, SH, CN, SCN, OCN,

In addition, R^m、Rⁿ、R^o、R^pIt can be with R⁷Or R⁸It is bonded and forms ring；

R⁹X⁹Y general formula (5)

R⁹For C_nH_aF_bCl_cBr_dI_e(CN)_f(SCN)_g(OCN)_h,

X⁹Selected from SO₂, C=O, C=S, R^qP=O, R^rP=S, S=O, Si=O,

R^q、R^rIt is each independently selected from hydrogen, halogen, the alkyl that can be substituted with a substituent, the cycloalkanes that can be substituted with a substituent Base, the unsaturated ring alkyl that can be substituted with a substituent, can be substituted base and take the unsaturated alkyl that can be substituted with a substituent The aromatic group in generation, the alkoxy that can be substituted with a substituent, can be substituted base at the heterocycle that can be substituted with a substituent Substituted unsaturated alkoxy, the thio alkoxy that can be substituted with a substituent, the unsaturation that can be substituted with a substituent are thio Alkoxy, OH, SH, CN, SCN, OCN,

In addition, R^q、R^rIt can be with R⁹It is bonded and forms ring,

Y is selected from O, S；

(R¹⁰X¹⁰)(R¹¹X¹¹)(R¹²X¹²) C general formula (6)

R¹⁰、R¹¹、R¹²It is each independently C_nH_aF_bCl_cBr_dI_e(CN)_f(SCN)_g(OCN)_h, n, a, b, c, d, e, f, g, h are respectively only On the spot it is 0 or more integer, meets 2n+1=a+b+c+d+e+f+g+h,

R¹⁰、R¹¹、R¹²In wantonly two can be bonded and form ring, at this point, formed ring group meet 2n=a+b+c+d+e+f+g+ H, in addition, R¹⁰、R¹¹、R¹²This 3 can be bonded and form ring, at this point, 2 in 3 group meets 2n=a+b+c+d+e+f+ G+h, 1 group meet 2n-1=a+b+c+d+e+f+g+h,

X¹⁰Selected from SO₂, C=O, C=S, R^sP=O, R^tP=S, S=O, Si=O,

X¹¹Selected from SO₂, C=O, C=S, R^uP=O, R^vP=S, S=O, Si=O,

X¹²Selected from SO₂, C=O, C=S, R^wP=O, R^xP=S, S=O, Si=O,

R^s、R^t、R^u、R^v、R^w、R^xIt is each independently selected from hydrogen, halogen, the alkyl that can be substituted with a substituent, base can be substituted Substituted naphthenic base, the unsaturated alkyl that can be substituted with a substituent, the unsaturated ring alkyl that can be substituted with a substituent, can be with The aromatic group that is substituted with a substituent, the heterocycle that can be substituted with a substituent, the alkoxy that can be substituted with a substituent, can With the unsaturated alkoxy that is substituted with a substituent, the thio alkoxy that can be substituted with a substituent, can be substituted with a substituent Unsaturated thio alkoxy, OH, SH, CN, SCN, OCN,

In addition, R^s、R^t、R^u、R^v、R^w、R^xIt can be with R¹⁰、R¹¹Or R¹²It is bonded and forms ring.

19. non-aqueous electrolyte secondary battery according to claim 1, wherein the cation of the salt is lithium.

20. non-aqueous electrolyte secondary battery according to claim 1, wherein the chemical structure of the anion of the salt by The following general formula (7), general formula (8) or general formula (9) expression,

(R¹³SO₂)(R¹⁴SO₂) N general formula (7)

R¹³、R¹⁴It is each independently C_nH_aF_bCl_cBr_dI_e,

N, a, b, c, d, e are each independently 0 or more integer, meet 2n+1=a+b+c+d+e,

In addition, R¹³And R¹⁴It can be mutually bonded and form ring, at this point, meeting 2n=a+b+c+d+e；

R¹⁵SO₃General formula (8)

R¹⁵For C_nH_aF_bCl_cBr_dI_e,

N, a, b, c, d, e are each independently 0 or more integer, meet 2n+1=a+b+c+d+e；

(R¹⁶SO₂)(R¹⁷SO₂)(R¹⁸SO₂) C general formula (9)

R¹⁶、R¹⁷、R¹⁸It is each independently C_nH_aF_bCl_cBr_dI_e,

N, a, b, c, d, e are each independently 0 or more integer, meet 2n+1=a+b+c+d+e,

R¹⁶、R¹⁷、R¹⁸In wantonly 2 can be bonded and form ring, at this point, formed ring group meet 2n=a+b+c+d+e, in addition, R¹⁶、R¹⁷、R¹⁸This 3 can be bonded and form ring, at this point, 2 in 3 group meets 2n=a+b+c+d+e, 1 group is full Sufficient 2n-1=a+b+c+d+e.

21. non-aqueous electrolyte secondary battery according to claim 1, wherein the salt is (CF₃SO₂)₂NLi、(FSO₂)₂NLi、(C₂F₅SO₂)₂NLi、FSO₂(CF₃SO₂)NLi、(SO₂CF₂CF₂SO₂)NLi、(SO₂CF₂CF₂CF₂SO₂)NLi、FSO₂ (CH₃SO₂)NLi、FSO₂(C₂F₅SO₂) NLi or FSO₂(C₂H₅SO₂)NLi。

22. non-aqueous electrolyte secondary battery according to claim 1, wherein the organic solvent is selected from acetonitrile or carbonic acid Dimethyl ester.

23. non-aqueous electrolyte secondary battery according to claim 1, wherein the organic solvent is selected from the following general formula (10) linear carbonate indicated,

R¹⁹OCOOR²⁰General formula (10)

R¹⁹、R²⁰It is each independently selected from the C of chain-like alkyl_nH_aF_bCl_cBr_dI_eWith contain cyclic alkyl in chemical structure C_mH_fF_gCl_hBr_iI_jAny of, n, a, b, c, d, e, m, f, g, h, i, j are each independently 0 or more integer, meet 2n+ 1=a+b+c+d+e, 2m-1=f+g+h+i+j.

24. non-aqueous electrolyte secondary battery according to claim 1, wherein the organic solvent be selected from dimethyl carbonate, Methyl ethyl carbonate or diethyl carbonate.

25. non-aqueous electrolyte secondary battery according to claim 1, wherein the relationship of the Io and the Is are Is > 2 ×Io。

26. non-aqueous electrolyte secondary battery according to claim 1, wherein meet the condition 1,

The organic solvent of the electrolyte is nitrile, amides, esters, ketone, acid anhydrides, sulfone class, nitro class or heterocycle Class.

27. non-aqueous electrolyte secondary battery according to claim 26, wherein the esters are carbonates, isocyanic acid Esters, cyclic annular esters or phosphoric acid ester.

28. non-aqueous electrolyte secondary battery according to claim 26, wherein the heterocyclic be epoxies,Azole, Furans, cyclic annular esters or heteroaromatic class.

29. non-aqueous electrolyte secondary battery according to claim 1, wherein meet the condition 1,

The organic solvent of the electrolyte is selected from acetonitrile, propionitrile, acrylonitrile, malononitrile, ethylene carbonate, polypropylene carbonate Ester, formamide, N,N-dimethylformamide, DMAC N,N' dimethyl acetamide, N-Methyl pyrrolidone, isopropyl isocyanate, just Propylisocyanate, chloromethane based isocyanate, methyl acetate, ethyl acetate, propyl acetate, methyl propionate, methyl formate, formic acid Ethyl ester, vinyl acetate, methyl acrylate, methyl methacrylate, Glycidyl methyl ether, epoxy butane, 2- ethyl epoxy Ethane,Azoles, 2- ethylAzoles,Oxazoline, 2- methyl -2-Oxazoline, acetone, methyl ethyl ketone, methyl iso-butyl ketone (MIBK), acetic acid Acid anhydride, propionic andydride, dimethyl sulfone, sulfolane, 1- nitropropane, 2- nitropropane, furans, furfural, gamma-butyrolacton, in γ-penta Ester, δ-valerolactone, thiophene, pyridine, tetrahydro-pyrokomane, 1- crassitude, N-methylmorpholine, trimethyl phosphate, tricresyl phosphate The linear carbonate that ethyl ester or the following general formula (10) indicate,

R¹⁹OCOOR²⁰General formula (10)

R¹⁹、R²⁰It is each independently selected from the C of chain-like alkyl_nH_aF_bCl_cBr_dI_eWith contain cyclic alkyl in chemical structure C_mH_fF_gCl_hBr_iI_jAny of, the integer that n is 1~6, the integer that m is 3~8, a, b, c, d, e, f, g, h, i, j are respectively only On the spot it is 0 or more integer, meets 2n+1=a+b+c+d+e, 2m-1=f+g+h+i+j.

30. non-aqueous electrolyte secondary battery according to claim 29, wherein the chain carbonic acid that the general formula (10) indicates Ester is dimethyl carbonate, diethyl carbonate or methyl ethyl carbonate.

31. non-aqueous electrolyte secondary battery according to claim 1, wherein meet the condition 1 or the condition 2,

The cation of the salt of the electrolyte is lithium,

The chemical structure of the anion of the salt by the following general formula (7) indicate,

(R¹³SO₂)(R¹⁴SO₂) N general formula (7)

R¹³、R¹⁴It is each independently C_nH_aF_bCl_cBr_dI_e,

N, a, b, c, d, e are each independently 0 or more integer, meet 2n+1=a+b+c+d+e,

In addition, R¹³And R¹⁴It can be mutually bonded and form ring, at this point, meet 2n=a+b+c+d+e,

The integer that n is 0~6, the R¹³And R¹⁴When being bonded and forming ring, n be 1~8 integer.

32. non-aqueous electrolyte secondary battery according to claim 1, wherein meet the condition 1 or the condition 2, it is right For the electrolyte,

The salt is selected from (CF₃SO₂)₂NLi、(FSO₂)₂NLi、(C₂F₅SO₂)₂NLi、FSO₂(CF₃SO₂)NLi、(SO₂CF₂CF₂SO₂) NLi、(SO₂CF₂CF₂CF₂SO₂)NLi、FSO₂(CH₃SO₂)NLi、FSO₂(C₂F₅SO₂) NLi or FSO₂(C₂H₅SO₂) NLi,

The organic solvent is selected from acetonitrile, propionitrile, acrylonitrile, tetrahydrofuran, 1,3- bis-Alkane, 1,4- bis-Alkane, 2- methyl four Hydrogen furans, ethylene carbonate, propylene carbonate, formamide, N,N-dimethylformamide, DMAC N,N' dimethyl acetamide, N- methyl Pyrrolidones, isopropyl isocyanate, n-propyl isocyanates, methyl acetate, ethyl acetate, propyl acetate, methyl propionate, first Sour methyl esters, Ethyl formate, vinyl acetate, methyl acrylate, methyl methacrylate,Azoles, acetone, methyl ethyl ketone, methyl are different Butyl ketone, acetic anhydride, propionic andydride, sulfolane, dimethyl sulfoxide, 1- nitropropane, 2- nitropropane, furans, furfural, γ-fourth Lactone, gamma-valerolactone, δ-valerolactone, thiophene, pyridine, 1- crassitude, N-methylmorpholine, trimethyl phosphate, tricresyl phosphate second The linear carbonate that ester or the following general formula (10) indicate,

R¹⁹OCOOR²⁰General formula (10)

33. non-aqueous electrolyte secondary battery according to claim 1, wherein meet the condition 1, for the electrolysis For liquid,

The organic solvent is selected from acetonitrile, propionitrile, acrylonitrile, ethylene carbonate, propylene carbonate, formamide, N, N- dimethyl Formamide, DMAC N,N' dimethyl acetamide, N-Methyl pyrrolidone, isopropyl isocyanate, n-propyl isocyanates, acetic acid first Ester, ethyl acetate, propyl acetate, methyl propionate, methyl formate, Ethyl formate, vinyl acetate, methyl acrylate, methyl-prop E pioic acid methyl ester,Azoles, acetone, methyl ethyl ketone, methyl iso-butyl ketone (MIBK), acetic anhydride, propionic andydride, sulfolane, 1- nitropropane, 2- nitre Base propane, furans, furfural, gamma-butyrolacton, gamma-valerolactone, δ-valerolactone, thiophene, pyridine, 1- crassitude, N- methyl The linear carbonate that quinoline, trimethyl phosphate, triethyl phosphate or the following general formula (10) indicate,

R¹⁹OCOOR²⁰General formula (10)

34. non-aqueous electrolyte secondary battery according to claim 1, wherein meet the condition 1,

The cation of the salt of the electrolyte is lithium,

(R¹³SO₂)(R¹⁴SO₂) N general formula (7)

R¹³、R¹⁴It is each independently C_nH_aF_bCl_cBr_dI_e,

N, a, b, c, d, e are each independently 0 or more integer, meet 2n+1=a+b+c+d+e,

The integer that n is 0~6, the R¹³And R¹⁴When being bonded and forming ring, n be 1~8 integer；

35. non-aqueous electrolyte secondary battery according to claim 34, wherein the esters are carbonates, isocyanic acid Esters, cyclic annular esters or phosphoric acid ester.

36. non-aqueous electrolyte secondary battery according to claim 34, wherein the heterocyclic be epoxies,Azole, Furans, cyclic annular esters or heteroaromatic class.

37. non-aqueous electrolyte secondary battery according to claim 1, wherein meet the condition 1,

The cation of the salt of the electrolyte is lithium,

(R¹³SO₂)(R¹⁴SO₂) N general formula (7)

R¹³、R¹⁴It is each independently C_nH_aF_bCl_cBr_dI_e,

N, a, b, c, d, e are each independently 0 or more integer, meet 2n+1=a+b+c+d+e,

R¹⁹OCOOR²⁰General formula (10)

38. the non-aqueous electrolyte secondary battery according to claim 37, wherein the chain carbonic acid that the general formula (10) indicates Ester is dimethyl carbonate, diethyl carbonate or methyl ethyl carbonate.

39. non-aqueous electrolyte secondary battery according to claim 1, wherein the anion of the salt of the electrolyte Chemical structure by the following general formula (7) indicate,

(R¹³SO₂)(R¹⁴SO₂) N general formula (7)

R¹³For F, R¹⁴For C_nH_aF_bCl_cBr_dI_e,

N, a, b, c, d, e are each independently 0 or more integer, meet 2n+1=a+b+c+d+e.

40. non-aqueous electrolyte secondary battery according to claim 39, wherein the salt of the electrolyte is (FSO₂)₂NLi、FSO₂(CF₃SO₂)NLi、FSO₂(CH₃SO₂)NLi、FSO₂(C₂F₅SO₂) NLi or FSO₂(C₂H₅SO₂)NLi。

41. non-aqueous electrolyte secondary battery according to claim 1, wherein meet the condition 1 and the condition 2.

42. non-aqueous electrolyte secondary battery according to claim 41, wherein the binder is polyacrylic acid.